Sample records for haloperoxidase reactions catalyzed

  1. Vanadium haloperoxidase-catalyzed bromination and cyclization of terpenes. (United States)

    Carter-Franklin, Jayme N; Parrish, Jon D; Tschirret-Guth, Richard A; Little, R Daniel; Butler, Alison


    Marine red algae (Rhodophyta) are a rich source of bioactive halogenated natural products, including cyclic terpenes. The biogenesis of certain cyclic halogenated marine natural products is thought to involve marine haloperoxidase enzymes. Evidence is presented that vanadium bromoperoxidase (V-BrPO) isolated and cloned from marine red algae that produce halogenated compounds (e.g., Plocamium cartilagineum, Laurencia pacifica, Corallina officinalis) can catalyze the bromination and cyclization of terpenes and terpene analogues. The V-BrPO-catalyzed reaction with the monoterpene nerol in the presence of bromide ion and hydrogen peroxide produces a monobromo eight-membered cyclic ether similar to laurencin, a brominated C15 acetogenin, from Laurencia glandulifera, along with noncyclic bromohydrin, epoxide, and dibromoproducts; however, reaction of aqueous bromine with nerol produced only noncyclic bromohydrin, epoxide, and dibromoproducts. The V-BrPO-catalyzed reaction with geraniol in the presence of bromide ion and hydrogen peroxide produces two singly brominated six-membered cyclic products, analogous to the ring structures of alpha and beta snyderols, brominated sesquiterpenes from Laurencia, spp., along with noncyclic bromohydrin, epoxide, and dibromoproducts; again, reaction of geraniol with aqueous bromine produces only noncyclic bromohydrin, epoxide, and dibromoproducts. Thus, V-BrPO can direct the electrophilic bromination and cyclization of terpenes.

  2. The Coprophilous Mushroom Coprinus radians Secretes a Haloperoxidase That Catalyzes Aromatic Peroxygenation▿ (United States)

    Anh, Dau Hung; Ullrich, René; Benndorf, Dirk; Svatoś, Aleś; Muck, Alexander; Hofrichter, Martin


    Coprophilous and litter-decomposing species (26 strains) of the genus Coprinus were screened for peroxidase activities by using selective agar plate tests and complex media based on soybean meal. Two species, Coprinus radians and C. verticillatus, were found to produce peroxidases, which oxidized aryl alcohols to the corresponding aldehydes at pH 7 (a reaction that is typical for heme-thiolate haloperoxidases). The peroxidase of Coprinus radians was purified to homogeneity and characterized. Three fractions of the enzyme, CrP I, CrP II, and CrP III, with molecular masses of 43 to 45 kDa as well as isoelectric points between 3.8 and 4.2, were identified after purification by anion-exchange and size exclusion chromatography. The optimum pH of the major fraction (CrP II) for the oxidation of aryl alcohols was around 7, and an H2O2 concentration of 0.7 mM was most suitable regarding enzyme activity and stability. The apparent Km values for ABTS [2,2′-azinobis(3-ethylbenzthiazolinesulfonic acid)], 2,6-dimethoxyphenol, benzyl alcohol, veratryl alcohol, and H2O2 were 49, 342, 635, 88, and 1,201 μM, respectively. The N terminus of CrP II showed 29% and 19% sequence identity to Agrocybe aegerita peroxidase (AaP) and chloroperoxidase, respectively. The UV-visible spectrum of CrP II was highly similar to that of resting-state cytochrome P450 enzymes, with the Soret band at 422 nm and additional maxima at 359, 542, and 571 nm. The reduced carbon monoxide complex showed an absorption maximum at 446 nm, which is characteristic of heme-thiolate proteins. CrP brominated phenol to 2- and 4-bromophenols and selectively hydroxylated naphthalene to 1-naphthol. Hence, after AaP, CrP is the second extracellular haloperoxidase-peroxygenase described so far. The ability to extracellularly hydroxylate aromatic compounds seems to be the key catalytic property of CrP and may be of general significance for the biotransformation of poorly available aromatic substances, such as lignin, humus

  3. The coprophilous mushroom Coprinus radians secretes a haloperoxidase that catalyzes aromatic peroxygenation. (United States)

    Anh, Dau Hung; Ullrich, René; Benndorf, Dirk; Svatos, Ales; Muck, Alexander; Hofrichter, Martin


    Coprophilous and litter-decomposing species (26 strains) of the genus Coprinus were screened for peroxidase activities by using selective agar plate tests and complex media based on soybean meal. Two species, Coprinus radians and C. verticillatus, were found to produce peroxidases, which oxidized aryl alcohols to the corresponding aldehydes at pH 7 (a reaction that is typical for heme-thiolate haloperoxidases). The peroxidase of Coprinus radians was purified to homogeneity and characterized. Three fractions of the enzyme, CrP I, CrP II, and CrP III, with molecular masses of 43 to 45 kDa as well as isoelectric points between 3.8 and 4.2, were identified after purification by anion-exchange and size exclusion chromatography. The optimum pH of the major fraction (CrP II) for the oxidation of aryl alcohols was around 7, and an H2O2 concentration of 0.7 mM was most suitable regarding enzyme activity and stability. The apparent Km values for ABTS [2,2'-azinobis(3-ethylbenzthiazolinesulfonic acid)], 2,6-dimethoxyphenol, benzyl alcohol, veratryl alcohol, and H2O2 were 49, 342, 635, 88, and 1,201 microM, respectively. The N terminus of CrP II showed 29% and 19% sequence identity to Agrocybe aegerita peroxidase (AaP) and chloroperoxidase, respectively. The UV-visible spectrum of CrP II was highly similar to that of resting-state cytochrome P450 enzymes, with the Soret band at 422 nm and additional maxima at 359, 542, and 571 nm. The reduced carbon monoxide complex showed an absorption maximum at 446 nm, which is characteristic of heme-thiolate proteins. CrP brominated phenol to 2- and 4-bromophenols and selectively hydroxylated naphthalene to 1-naphthol. Hence, after AaP, CrP is the second extracellular haloperoxidase-peroxygenase described so far. The ability to extracellularly hydroxylate aromatic compounds seems to be the key catalytic property of CrP and may be of general significance for the biotransformation of poorly available aromatic substances, such as lignin

  4. Thermodynamics of Enzyme-Catalyzed Reactions Database (United States)

    SRD 74 Thermodynamics of Enzyme-Catalyzed Reactions Database (Web, free access)   The Thermodynamics of Enzyme-Catalyzed Reactions Database contains thermodynamic data on enzyme-catalyzed reactions that have been recently published in the Journal of Physical and Chemical Reference Data (JPCRD). For each reaction the following information is provided: the reference for the data, the reaction studied, the name of the enzyme used and its Enzyme Commission number, the method of measurement, the data and an evaluation thereof.

  5. Palladium-catalyzed coupling reactions

    CERN Document Server

    Molnár, Árpád


    This handbook and ready reference brings together all significant issues of practical importance for interested readers in one single volume. While covering homogeneous and heterogeneous catalysis, the text is unique in focusing on such important aspects as using different reaction media, microwave techniques or catalyst recycling. It also provides a comprehensive treatment of modern-day coupling reactions and emphasizes those topics that show potential for future development, such as continuous flow systems, water as a reaction medium, and catalyst immobilization, among others. With i

  6. Improvement of the stability and activity of the BPO-A1 haloperoxidase from Streptomyces aureofaciens by directed evolution. (United States)

    Yamada, Ryosuke; Higo, Tatsutoshi; Yoshikawa, Chisa; China, Hideyasu; Ogino, Hiroyasu


    Haloperoxidases are oxygenases that catalyze the halogenation of a range of organic compounds without the need for additional high-cost cofactors. Thus, haloperoxidases with high activity and stability are desired for industrial application. In this study, a directed evolution approach was adopted to improve the thermostability of the homodimeric BPO-A1 haloperoxidase from Streptomyces aureofaciens. Among 1000 mutant BPO-A1 haloperoxidases, 2 mutants HT177 and HT507, having higher thermostabilities than the wild-type BPO-A1 haloperoxidase, were obtained by directed evolution. The residual activities of mutants HT177 and HT507 were 2.3- and 5.1-fold higher than that of wild-type BPO-A1, respectively, after incubation at 80 °C for 1 h. In addition, mutant HT177 showed higher stability in organic solvents, such as methanol, ethanol, dimethyl sulfoxide, and N,N-dimethylformamide, than the wild-type BPO-A1 haloperoxidase. Furthermore, mutant HT507 showed higher specific activity. Based on the evaluation of single-amino-acid-substituted mutants, stabilization of the α-helix conformation, substitution of amino acid residues located at the surface of the protein molecule, and enhancement of the interaction between subunits may account for the improvement in thermostability, organic solvent stability, and specific activity. Consequently, the thermostability, organic solvent stability, and specific activity of S. aureofaciens BPO-A1 haloperoxidase were successfully improved by a directed evolution approach.

  7. Chiral Diamine-catalyzed Asymmetric Aldol Reaction

    Institute of Scientific and Technical Information of China (English)

    LI Hui; XU Da-zhen; WU Lu-lu; WANG Yong-mei


    A highly efficient catalytic system composed of a simple and commercially available chiral primary diamine (1R,2R)-cyclohexane-1,2-diamine(6) and trifluoroacetic acid(TFA) was employed for asymmetric Aldol reaction in i-PrOH at room temperature.A loading of 10%(molar fraction) catalyst 6 with TFA as a cocatalyst could catalyze the Aldol reactions of various ketones or aldehydes with a series of aromatic aldehydes,furnishing Aldol products in moderate to high yields(up to >99%) with enantioselectivities of up to >99% and diastereoselectivities of up to 99:1.

  8. Heterogeneously Catalyzed Oxidation Reactions Using Molecular Oxygen

    DEFF Research Database (Denmark)

    Beier, Matthias Josef

    with a carboxylic acid resulting in TONs of up to 2000. In the absence of the carboxylic acid, ceria inhibited the reaction exhibiting radical scavenger properties. Contrary to p-xylene, neither ethylbenzene nor cumene conversion was promoted by ceria even in the presence of a carboxylic acid. Substantial leaching......Heterogeneously catalyzed selective oxidation reactions have attracted a lot of attention in recent time. The first part of the present thesis provides an overview over heterogeneous copper and silver catalysts for selective oxidations in the liquid phase and compared the performance and catalytic...... that both copper and silver can function as complementary catalyst materials to gold showing different catalytic properties and being more suitable for hydrocarbon oxidation reactions. Potential opportunities for future research were outlined. In an experimental study, the potential of silver as a catalyst...

  9. Biginelli Reaction Catalyzed by Copper Nanoparticles (United States)

    Dewan, Manika; Kumar, Ajeet; Saxena, Amit; De, Arnab; Mozumdar, Subho


    We recently reported a novel synthesis of copper nanoparticles from copper sulphate utilizing the charge-compensatory effect of ionic liquid [bmim]BF4 and ethylene glycol. The nanoparticles were characterized and found to be stable for one year. Here we hypothesize that the stabilized nanoparticles should be able to catalyze one-pot multicomponent organic reactions. We show that the nanoparticles catalyzed Biginelli reaction at room temperature to give the product 3,4-dihydopyrimidinone (>90% yield in ∼15 minutes) from aldehydes, β-diketoester (ethylacetoacetate) and urea (or thiourea). ). Remarkably, such high yields and rapid kinetics was found to be independent of the electronic density on the reactant aryl-aldehyde. This was probably because even the surface-active particles reacted faster in the presence of ionic liquid as compared to conventional methods. The heterocyclic dihydropyrimidinones (DHPMs) and their derivatives are widely used in natural and synthetic organic chemistry due to their wide spectrum of biological and therapeutic properties (resulting from their antibacterial, antiviral, antitumor and anti-inflammatory activities. Our method has an easy work-up procedure and the nanoparticles could be recycled with minimal loss of efficiency. PMID:22912792

  10. [Thymidylate synthase-catalyzed reaction mechanism]. (United States)

    Rode, Wojciech; Jarmuńa, Adam


    Thymidylate synthase ThyA (EC;-encoded by the Tyms gene), having been for 60 years a molecular target in chemotherapy, catalyses the dUMP pyrimidine ring C(5) methylation reaction, encompassing a transfer of one-carbon group (the methylene one, thus at the formaldehyde oxidation level) from 6R-N5,10-methylenetetrahydrofolate, coupled with a reduction of this group to the methyl one, with concomitant generation of 7,8-dihydrofolate and thymidylate. New facts are presented, concerning (i) molecular mechanism of the catalyzed reaction, including the substrate selectivity mechanism, (ii) mechanism of inhibition by a particular inhibitor, N4-hydroxy-dCMP, (iii) structural properties of the enzyme, (iv) cellular localization, (v) potential posttranslational modifications of the enzyme protein and their influence on the catalytic properties and (vi) non-catalytic activities of the enzyme.

  11. Representing Rate Equations for Enzyme-Catalyzed Reactions (United States)

    Ault, Addison


    Rate equations for enzyme-catalyzed reactions are derived and presented in a way that makes it easier for the nonspecialist to see how the rate of an enzyme-catalyzed reaction depends upon kinetic constants and concentrations. This is done with distribution equations that show how the rate of the reaction depends upon the relative quantities of…

  12. Zinc catalyzed Guanylation reaction of Amines with Carbodiimides ...

    Indian Academy of Sciences (India)

    016-1096-y. Zinc catalyzed Guanylation reaction of Amines with Carbodiimides/. Isocyanate leading to Guanidines/Urea derivatives formation. JAYEETA BHATTACHARJEE, MITALI SACHDEVA, INDRANI BANERJEE and. TARUN K PANDA.

  13. Metal-catalyzed asymmetric aldol reactions

    Energy Technology Data Exchange (ETDEWEB)

    Dias, Luiz C.; Lucca Junior, Emilio C. de; Ferreira, Marco A. B.; Polo, Ellen C., E-mail: [Universidade de Campinas (UNICAMP), SP (Brazil). Inst. de Quimica


    The aldol reaction is one of the most powerful and versatile methods for the construction of C-C bonds. Traditionally, this reaction was developed in a stoichiometric version; however, great efforts in the development of chiral catalysts for aldol reactions were performed in recent years. Thus, in this review article, the development of metal-mediated chiral catalysts in Mukaiyama-type aldol reaction, reductive aldol reaction and direct aldol reaction are discussed. Moreover, the application of these catalysts in the total synthesis of complex molecules is discussed. (author)

  14. Cyclodextrin-Catalyzed Organic Synthesis: Reactions, Mechanisms, and Applications

    Directory of Open Access Journals (Sweden)

    Chang Cai Bai


    Full Text Available Cyclodextrins are well-known macrocyclic oligosaccharides that consist of α-(1,4 linked glucose units and have been widely used as artificial enzymes, chiral separators, chemical sensors, and drug excipients, owing to their hydrophobic and chiral interiors. Due to their remarkable inclusion capabilities with small organic molecules, more recent interests focus on organic reactions catalyzed by cyclodextrins. This contribution outlines the current progress in cyclodextrin-catalyzed organic reactions. Particular emphases are given to the organic reaction mechanisms and their applications. In the end, the future directions of research in this field are proposed.

  15. Recent advances in copper-catalyzed asymmetric coupling reactions

    Directory of Open Access Journals (Sweden)

    Fengtao Zhou


    Full Text Available Copper-catalyzed (or -mediated asymmetric coupling reactions have received significant attention over the past few years. Especially the coupling reactions of aryl or alkyl halides with nucleophiles became a very powerful tool for the formation of C–C, C–N, C–O and other carbon–heteroatom bonds as well as for the construction of heteroatom-containing ring systems. This review summarizes the recent progress in copper-catalyzed asymmetric coupling reactions for the formation of C–C and carbon–heteroatom bonds.

  16. Structure and function of vanadium haloperoxidases

    NARCIS (Netherlands)

    Wever, R.; Michibata, H.


    Vanadium haloperoxidases contain the bare metal oxide vanadate as a prosthetic group and differ strongly from the heme peroxidases in substrate specificity and molecular properties. The substrates of these enzymes are limited to halides and sulfides, which in the presence of hydrogen peroxide are

  17. Method for predicting enzyme-catalyzed reactions (United States)

    Hlavacek, William S.; Unkefer, Clifford J.; Mu, Fangping; Unkefer, Pat J.


    The reactivity of given metabolites is assessed using selected empirical atomic properties in the potential reaction center. Metabolic reactions are represented as biotransformation rules. These rules are generalized from the patterns in reactions. These patterns are not unique to reactants but are widely distributed among metabolites. Using a metabolite database, potential substructures are identified in the metabolites for a given biotransformation. These substructures are divided into reactants or non-reactants, depending on whether they participate in the biotransformation or not. Each potential substructure is then modeled using descriptors of the topological and electronic properties of atoms in the potential reaction center; molecular properties can also be used. A Support Vector Machine (SVM) or classifier is trained to classify a potential reactant as a true or false reactant using these properties.

  18. Palladium-Catalyzed, Enantioselective Heine Reaction. (United States)

    Punk, Molly; Merkley, Charlotte; Kennedy, Katlyn; Morgan, Jeremy B


    Aziridines are important synthetic intermediates for the generation of nitrogen-containing molecules. N-Acylaziridines undergo rearrangement by ring expansion to produce oxazolines, a process known as the Heine reaction. The first catalytic, enantioselective Heine reaction is reported for meso-N-acylaziridines where a palladium(II)-diphosphine complex is employed. The highly enantioenriched oxazoline products are valuable organic synthons and potential ligands for transition-metal catalysis.

  19. Transfer hydrogenation reactions catalyzed by chiral half-sandwich ...

    Indian Academy of Sciences (India)

    oxidoreductases catalyze transfer hydrogenation of car- ... ruthenium(II) complexes containing (S)-N-substituted- ... 2. Experimental. 2.1 Materials and methods. All reactions and manipulations were routinely per- formed under a nitrogen atmosphere using standard. Schlenk techniques in oven-dried glassware. L-Proline,.

  20. Development of a Lewis Base Catalyzed Selenocyclization Reaction (United States)

    Collins, William


    The concept of Lewis base activation of selenium Lewis acids has been effectively reduced to practice in the Lewis base catalyzed selenofunctionalization of unactivated olefins. In this reaction, the weakly acidic species, "N"-phenylselenyl succinimide, is cooperatively activated by the addition of a "soft" Lewis base donor (phosphine sulfides,…

  1. (Ligand intermediates in metal-catalyzed reactions)

    Energy Technology Data Exchange (ETDEWEB)


    This report consists of sections on sigma bond complexes of alkenes, a new carbon-hydrogen bond activation reaction of alkene complexes, carbon-hydrogen bond migrations in alkylidene complexes, carbon- hydrogen bond migrations in alkyne complexes, synthesis, structure and reactivity of C{sub x} complexes, synthesis and reactivity of alcohol and ether complexes, new catalysts for the epimerization of secondary alcohols; carbon-hydrogen bond activation in alkoxide complexes, pi/sigma equilibria in metal/O=CXX' complexes, and other hydrocarbon ligands; miscellaneous.(WET)

  2. Studies on the use of haloperoxidases in organic synthesis

    NARCIS (Netherlands)

    Franssen, M.C.R.


    The subject of this thesis is the use of haloperoxidases in synthetic organic chemistry. Haloperoxidases are enzymes capable of halogenating a variety of organic compounds. They require hydrogen peroxide and halide ions as cosubstrates. The enzymes operate under mild conditions, compared to

  3. Mild and efficient cyanuric chloride catalyzed Pictet–Spengler reaction

    Directory of Open Access Journals (Sweden)

    Ashish Sharma


    Full Text Available A practical, mild and efficient protocol for the Pictet–Spengler reaction catalyzed by cyanuric chloride (trichloro-1,3,5-triazine, TCT is described. The 6-endo cyclization of tryptophan/tryptamine and modified Pictet–Spengler substrates with both electron-withdrawing and electron-donating aldehydes was carried out by using a catalytic amount of TCT (10 mol % in DMSO under a nitrogen atmosphere. TCT catalyzed the Pictet–Spengler reaction involving electron-donating aldehydes in excellent yield. Thus, it has a distinct advantage over the existing methodologies where electron-donating aldehydes failed to undergo 6-endo cyclization. Our methodology provided broad substrate scope and diversity. This is indeed the first report of the use of TCT as a catalyst for the Pictet–Spengler reaction.

  4. Asymmetric Stetter reactions catalyzed by thiamine diphosphate-dependent enzymes. (United States)

    Kasparyan, Elena; Richter, Michael; Dresen, Carola; Walter, Lydia S; Fuchs, Georg; Leeper, Finian J; Wacker, Tobias; Andrade, Susana L A; Kolter, Geraldine; Pohl, Martina; Müller, Michael


    The intermolecular asymmetric Stetter reaction is an almost unexplored transformation for biocatalysts. Previously reported thiamine diphosphate (ThDP)-dependent PigD from Serratia marcescens is the first enzyme identified to catalyze the Stetter reaction of α,β-unsaturated ketones (Michael acceptor substrates) and α-keto acids. PigD is involved in the biosynthesis of the potent cytotoxic agent prodigiosin. Here, we describe the investigation of two new ThDP-dependent enzymes, SeAAS from Saccharopolyspora erythraea and HapD from Hahella chejuensis. Both show a high degree of homology to the amino acid sequence of PigD (39 and 51 %, respectively). The new enzymes were heterologously overproduced in Escherichia coli, and the yield of soluble protein was enhanced by co-expression of the chaperone genes groEL/ES. SeAAS and HapD catalyze intermolecular Stetter reactions in vitro with high enantioselectivity. The enzymes possess a characteristic substrate range with respect to Michael acceptor substrates. This provides support for a new type of ThDP-dependent enzymatic activity, which is abundant in various species and not restricted to prodigiosin biosynthesis in different strains. Moreover, PigD, SeAAS, and HapD are also able to catalyze asymmetric carbon-carbon bond formation reactions of aldehydes and α-keto acids, resulting in 2-hydroxy ketones.

  5. Enantioselective aldol reactions catalyzed by chiral phosphine oxides. (United States)

    Kotani, Shunsuke; Sugiura, Masaharu; Nakajima, Makoto


    The development of enantioselective aldol reactions catalyzed by chiral phosphine oxides is described. The aldol reactions presented herein do not require the prior preparation of the masked enol ethers from carbonyl compounds as aldol donors. The reactions proceed through a trichlorosilyl enol ether intermediate, formed in situ from carbonyl compounds, which then acts as the aldol donor. Phosphine oxides activate the trichlorosilyl enol ethers to afford the aldol adducts with high stereoselectivities. This procedure was used to realize a directed cross-aldol reaction between ketones and two types of double aldol reactions (a reaction at one/two α position(s) of a carbonyl group) with high diastereo- and enantioselectivities. Copyright © 2013 The Chemical Society of Japan and Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Mechanism of the reaction catalyzed by mandelate racemase. 3. Asymmetry in reactions catalyzed by the H297N mutant

    Energy Technology Data Exchange (ETDEWEB)

    Landro, J.A.; Kallarakal, A.T.; Ransom, S.C.; Gerlt, J.A.; Kozarich, J.W. (Univ. of Maryland, College Park (United States)); Neidhart, D.J. (Abbott Labs., Abbott Park, IL (United States)); Kenyon, G.L. (Univ. of California, San Francisco (United States))


    Two preceding papers suggest that the active site of mandelate racemase (MR) contains two distinct general acid/base catalysts: Lys 166, which abstracts the {alpha}-proton from (s)-mandelate, and His 297, which abstracts the {alpha}-proton from (R)-mandelate. In this paper the authors report on the properties of the mutant of MR in which His 297 has been converted to asparagine by site-directed mutagenesis (H297N). The structure of H297N, solved by molecular replacement at 2.2-{angstrom} resolution, reveals that no conformational alterations accompany the substitution. As expected, h297N has no detectable MR activity. However, H297N catalyzes the stereospecific elimination of bromide ion from racemic {rho}-(bromomethyl) mandelate to give {rho}-(methyl)-benzoylformate in 45% yield at a rate equal to that measured for wild-type enzyme. The pD dependence of the rate of the exchange reaction catalyzed by H297N reveals a pK{sub a} of 6.4 in D{sub 2}O which is assigned to Lys 166. These observations provide persuasive evidence that the reaction catalyzed by MR does, in fact, proceed via a two-base mechanism in which Lys 166 abstracts the {alpha}-proton from (S)-mandelate and His 297 abstracts the {alpha}-proton from (R)-mandelate. These studies demonstrate the power of site-directed mutagenesis in providing otherwise inaccessible detail about the mechanism of an enzyme-catalyzed reaction.

  7. Gold-catalyzed cyclization reactions of allenol and alkynol derivatives. (United States)

    Alcaide, Benito; Almendros, Pedro


    Although gold is chemically inert as a bulk metal, the landmark discovery that gold nanoparticles can be effective catalysts has opened up new and exciting research opportunities in the field. In recent years, there has been growth in the number of reactions catalyzed by gold complexes [gold(I) and gold(III)], usually as homogeneous catalysts, because they are soft Lewis acids. In addition, alkynes and allenes have interesting reactivities and selectivities, notably their ability to produce complex structures in very few steps. In this Account, we describe our work in gold catalysis with a focus on the formation of C-C and C-O bonds using allenes and alkynes as starting materials. Of these, oxa- and carbo-cyclizations are perhaps the best known and most frequently studied. We have divided those contributions into sections arranged according to the nature of the starting material (allene versus alkyne). Gold-catalyzed carbocyclizations in allenyl C2-linked indoles, allenyl-β-lactams, and allenyl sugars follow different mechanistic pathways. The cyclization of indole-tethered allenols results in the efficient synthesis of carbazole derivatives, for example. However, the compound produced from gold-catalyzed 9-endo carbocyclization of (aryloxy)allenyl-tethered 2-azetidinones is in noticeable contrast to the 5-exo hydroalkylation product that results from allenyl sugars. We have illustrated the unusual preference for the 4-exo-dig cyclization in allene chemistry, as well as the rare β-hydride elimination reaction, in gold catalysis from readily available α-allenols. We have also observed in γ-allenols that a (methoxymethyl)oxy protecting group not only masks a hydroxyl functionality but also exerts directing effects as a controlling unit in a gold-catalyzed regioselectivity reversal. Our recent work has also led to a combined experimental and computational study on regioselective gold-catalyzed synthetic routes to 1,3-oxazinan-2-ones (kinetically controlled

  8. Deoxyribonucleoside kinases: two enzyme families catalyze the same reaction. (United States)

    Sandrini, Michael P B; Piskur, Jure


    Mammals have four deoxyribonucleoside kinases, the cytoplasmic (TK1) and mitochondrial (TK2) thymidine kinases, and the deoxycytidine (dCK) and deoxyguanosine (dGK) kinases, which salvage the precursors for nucleic acids synthesis. In addition to the native deoxyribonucleoside substrates, the kinases can phosphorylate and thereby activate a variety of anti-cancer and antiviral prodrugs. Recently, the crystal structure of human TK1 has been solved and has revealed that enzymes with fundamentally different origins and folds catalyze similar, crucial cellular reactions.

  9. Clay-catalyzed reactions of coagulant polymers during water chlorination (United States)

    Lee, J.-F.; Liao, P.-M.; Lee, C.-K.; Chao, H.-P.; Peng, C.-L.; Chiou, C.T.


    The influence of suspended clay/solid particles on organic-coagulant reactions during water chlorination was investigated by analyses of total product formation potential (TPFP) and disinfection by-product (DBP) distribution as a function of exchanged clay cation, coagulant organic polymer, and reaction time. Montmorillonite clays appeared to act as a catalytic center where the reaction between adsorbed polymer and disinfectant (chlorine) was mediated closely by the exchanged clay cation. The transition-metal cations in clays catalyzed more effectively than other cations the reactions between a coagulant polymer and chlorine, forming a large number of volatile DBPs. The relative catalytic effects of clays/solids followed the order Ti-Mont > Fe-Mont > Cu-Mont > Mn-Mont > Ca-Mont > Na-Mont > quartz > talc. The effects of coagulant polymers on TPFP follow the order nonionic polymer > anionic polymer > cationic polymer. The catalytic role of the clay cation was further confirmed by the observed inhibition in DBP formation when strong chelating agents (o-phenanthroline and ethylenediamine) were added to the clay suspension. Moreover, in the presence of clays, total DBPs increased appreciably when either the reaction time or the amount of the added clay or coagulant polymer increased. For volatile DBPs, the formation of halogenated methanes was usually time-dependent, with chloroform and dichloromethane showing the greatest dependence. ?? 2003 Elsevier Inc. All rights reserved.

  10. Time-dependent kinetic complexities in cholinesterase-catalyzed reactions. (United States)

    Masson, P


    Cholinesterases (ChEs) display a hysteretic behavior with certain substrates and inhibitors. Kinetic cooperativity in hysteresis of ChE-catalyzed reactions is characterized by a lag or burst phase in the approach to steady state. With some substrates damped oscillations are shown to superimpose on hysteretic lags. These time dependent peculiarities are observed for both butyrylcholinesterase and acetylcholinesterase from different sources. Hysteresis in ChE-catalyzed reactions can be interpreted in terms of slow transitions between two enzyme conformers E and E'. Substrate can bind to E and/or E', both Michaelian complexes ES and Ε'S can be catalytically competent, or only one of them can make products. The formal reaction pathway depends on both the chemical structure of the substrate and the type of enzyme. In particular, damped oscillations develop when substrate exists in different, slowly interconvertible, conformational, and/or micellar forms, of which only the minor form is capable of binding and reacting with the enzyme. Biphasic pseudo-first-order progressive inhibition of ChEs by certain carbamates and organophosphates also fits with a slow equilibrium between two reactive enzyme forms. Hysteresis can be modulated by medium parameters (pH, chaotropic and kosmotropic salts, organic solvents, temperature, osmotic pressure, and hydrostatic pressure). These studies showed that water structure plays a role in hysteretic behavior of ChEs. Attempts to provide a molecular mechanism for ChE hysteresis from mutagenesis studies or crystallographic studies failed so far. In fact, several lines of evidence suggest that hysteresis is controlled by the conformation of His438, a key residue in the catalytic triad of cholinesterases. Induction time may depend on the probability of His438 to adopt the operative conformation in the catalytic triad. The functional significance of ChE hysteresis is puzzling. However, the accepted view that proteins are in equilibrium between

  11. Recent advances in osmium-catalyzed hydrogenation and dehydrogenation reactions. (United States)

    Chelucci, Giorgio; Baldino, Salvatore; Baratta, Walter


    CONSPECTUS: A current issue in metal-catalyzed reactions is the search for highly efficient transition-metal complexes affording high productivity and selectivity in a variety of processes. Moreover, there is also a great interest in multitasking catalysts that are able to efficiently promote different organic transformations by careful switching of the reaction parameters, such as temperature, solvent, and cocatalyst. In this context, osmium complexes have shown the ability to catalyze efficiently different types of reactions involving hydrogen, proving at the same time high thermal stability and simple synthesis. In the catalytic reduction of C═X (X = O, N) bonds by both hydrogenation (HY) and transfer hydrogenation (TH) reactions, the most interest has been focused on homogeneous systems based on rhodium, iridium, and in particular ruthenium catalysts, which have proved to catalyze chemo- and stereoselective hydrogenations with remarkable efficiency. By contrast, osmium catalysts have received much less attention because they are considered less active on account of their slower ligand exchange kinetics. Thus, this area remained almost neglected until recent studies refuted these prejudices. The aim of this Account is to highlight the impressive developments achieved over the past few years by our and other groups on the design of new classes of osmium complexes and their applications in homogeneous catalytic reactions involving the hydrogenation of carbon-oxygen and carbon-nitrogen bonds by both HY and TH reactions as well as in alcohol deydrogenation (DHY) reactions. The work described in this Account demonstrates that osmium complexes are emerging as powerful catalysts for asymmetric and non-asymmetric syntheses, showing a remarkably high catalytic activity in HY and TH reactions of ketones, aldehydes, imines, and esters as well in DHY reactions of alcohols. Thus, for instance, the introduction of ligands with an NH function, possibly in combination with a

  12. Enzyme catalyzed reactions: from experiment to computational mechanism reconstruction. (United States)

    Srividhya, Jeyaraman; Mourão, Márcio A; Crampin, Edmund J; Schnell, Santiago


    The traditional experimental practice in enzyme kinetics involves the measurement of substrate or product concentrations as a function of time. Advances in computing have produced novel approaches for modeling enzyme catalyzed reactions from time course data. One example of such an approach is the selection of appropriate chemical reactions that best fit the data. A common limitation of this approach resides in the number of chemical species considered. The number of possible chemical reactions grows exponentially with the number of chemical species, which makes difficult to select reactions that uniquely describe the data and diminishes the efficiency of the methods. In addition, a method's performance is also dependent on several quantitative and qualitative properties of the time course data, of which we know very little. This information is important to experimentalists as it could allow them to setup their experiments in ways that optimize the network reconstruction. We have previously described a method for inferring reaction mechanisms and kinetic rate parameters from time course data. Here, we address the limitations in the number of chemical reactions by allowing the introduction of information about chemical interactions. We also address the unknown properties of the input data by determining experimental data properties that maximize our method's performance. We investigate the following properties: initial substrate-enzyme concentration ratios; initial substrate-enzyme concentration variation ranges; number of data points; number of different experiments (time courses); and noise. We test the method using data generated in silico from the Michaelis-Menten and the Hartley-Kilby reaction mechanisms. Our results demonstrate the importance of experimental design for time course assays that has not been considered in experimental protocols. These considerations can have far reaching implications for the computational mechanism reconstruction process

  13. Fe(II)/Fe(III)-Catalyzed Intramolecular Didehydro-Diels-Alder Reaction of Styrene-ynes. (United States)

    Mun, Hyeon Jin; Seong, Eun Young; Ahn, Kwang-Hyun; Kang, Eun Joo


    The intramolecular didehydro-Diels-Alder reaction of styrene-ynes was catalyzed by Fe(II) and Fe(III) to produce various naphthalene derivatives under microwave heating conditions. Mechanistic calculations found that the Fe(II) catalyst activates the styrenyl diene in an inverse-electron-demand Diels-Alder reaction, and the consecutive dehydrogenation reaction can be promoted by either Fe(II)-catalyzed direct dehydrogenation or an Fe(III)-catalyzed rearomatization/dehydrogenation pathway.

  14. The enzymatic reaction catalyzed by lactate dehydrogenase exhibits one dominant reaction path (United States)

    Masterson, Jean E.; Schwartz, Steven D.


    Enzymes are the most efficient chemical catalysts known, but the exact nature of chemical barrier crossing in enzymes is not fully understood. Application of transition state theory to enzymatic reactions indicates that the rates of all possible reaction paths, weighted by their relative probabilities, must be considered in order to achieve an accurate calculation of the overall rate. Previous studies in our group have shown a single mechanism for enzymatic barrier passage in human heart lactate dehydrogenase (LDH). To ensure that this result was not due to our methodology insufficiently sampling reactive phase space, we implement high-perturbation transition path sampling in both microcanonical and canonical regimes for the reaction catalyzed by human heart LDH. We find that, although multiple, distinct paths through reactive phase space are possible for this enzymatic reaction, one specific reaction path is dominant. Since the frequency of these paths in a canonical ensemble is inversely proportional to the free energy barriers separating them from other regions of phase space, we conclude that the rarer reaction paths are likely to have a negligible contribution. Furthermore, the non-dominate reaction paths correspond to altered reactive conformations and only occur after multiple steps of high perturbation, suggesting that these paths may be the result of non-biologically significant changes to the structure of the enzymatic active site.

  15. Enantioconvergent synthesis by sequential asymmetric Horner-Wadsworth-Emmons and palladium-catalyzed allylic substitution reactions

    DEFF Research Database (Denmark)

    Pedersen, Torben Møller; Hansen, E. Louise; Kane, John


    A new method for enantioconvergent synthesis has been developed. The strategy relies on the combination of an asymmetric Horner-Wadsworth-Emmons (HWE) reaction and a palladium-catalyzed allylic substitution. Different $alpha@-oxygen-substituted, racemic aldehydes were initially transformed...... by asymmetric HWE reactions into mixtures of two major $alpha@,$beta@-unsaturated esters, possessing opposite configurations at their allylic stereocenters as well as opposite alkene geometry. Subsequently, these isomeric mixtures of alkenes could be subjected to palladium-catalyzed allylic substitution...

  16. Gold(III)-catalyzed three-component coupling reaction (TCC) selective toward furans. (United States)

    Li, Jian; Liu, Li; Ding, Dong; Sun, Jiangtao; Ji, Yangxuan; Dong, Jialing


    An efficient three-component coupling reaction toward a variety of furan derivatives has been developed. This cascade transformation proceeds via the gold-catalyzed coupling reaction of phenylglyoxal derivatives, secondary amines, and terminal alkynes, under the reaction conditions, that undergoes cyclization into the furan core.

  17. Recent developments in gold-catalyzed cycloaddition reactions

    Directory of Open Access Journals (Sweden)

    Fernando López


    Full Text Available In the last years there have been extraordinary advances in the development of gold-catalyzed cycloaddition processes. In this review we will summarize some of the most remarkable examples, and present the mechanistic rational underlying the transformations.

  18. Exploring the chemistry and biology of vanadium-dependent haloperoxidases. (United States)

    Winter, Jaclyn M; Moore, Bradley S


    Nature has developed an exquisite array of methods to introduce halogen atoms into organic compounds. Most of these enzymes are oxidative and require either hydrogen peroxide or molecular oxygen as a cosubstrate to generate a reactive halogen atom for catalysis. Vanadium-dependent haloperoxidases contain a vanadate prosthetic group and utilize hydrogen peroxide to oxidize a halide ion into a reactive electrophilic intermediate. These metalloenzymes have a large distribution in nature, where they are present in macroalgae, fungi, and bacteria, but have been exclusively characterized in eukaryotes. In this minireview, we highlight the chemistry and biology of vanadium-dependent haloperoxidases from fungi and marine algae and the emergence of new bacterial members that extend the biological function of these poorly understood halogenating enzymes.

  19. Exploring the Chemistry and Biology of Vanadium-dependent Haloperoxidases* (United States)

    Winter, Jaclyn M.; Moore, Bradley S.


    Nature has developed an exquisite array of methods to introduce halogen atoms into organic compounds. Most of these enzymes are oxidative and require either hydrogen peroxide or molecular oxygen as a cosubstrate to generate a reactive halogen atom for catalysis. Vanadium-dependent haloperoxidases contain a vanadate prosthetic group and utilize hydrogen peroxide to oxidize a halide ion into a reactive electrophilic intermediate. These metalloenzymes have a large distribution in nature, where they are present in macroalgae, fungi, and bacteria, but have been exclusively characterized in eukaryotes. In this minireview, we highlight the chemistry and biology of vanadium-dependent haloperoxidases from fungi and marine algae and the emergence of new bacterial members that extend the biological function of these poorly understood halogenating enzymes. PMID:19363038

  20. Modeling of mass transfer in combination with a homogeneously catalyzed reaction

    NARCIS (Netherlands)

    Hoorn, J.A.A.; Versteeg, G. F.

    The mass transfer rates of a gaseous reactant into a liquid where the reactions are catalyzed by homogeneous catalysts have been evaluated by the numerical solution of the diffusion-reaction equations according to Higbie's penetration theory. The concentration profiles as well as enhancement factors

  1. Mechanism of Cytochrome P450 17A1-Catalyzed Hydroxylase and Lyase Reactions

    DEFF Research Database (Denmark)

    Bonomo, Silvia; Jorgensen, Flemming Steen; Olsen, Lars


    Cytochrome P450 17A1 (CYP17A1) catalyzes C17 hydroxylation of pregnenolone and progesterone and the subsequent C17–C20 bond cleavage (lyase reaction) to form androgen precursors. Compound I (Cpd I) and peroxo anion (POA) are the heme-reactive species underlying the two reactions. We have...

  2. Palladium(0)/NHC-Catalyzed Reductive Heck Reaction of Enones : A Detailed Mechanistic Study

    NARCIS (Netherlands)

    Raoufmoghaddam, Saeed; Mannathan, Subramaniyan; Minnaard, Adriaan J; de Vries, Johannes G; Reek, Joost N H


    We have studied the mechanism of the palladium-catalyzed reductive Heck reaction of para-substituted enones with 4-iodoanisole by using N,N-diisopropylethylamine (DIPEA) as the reductant. Kinetic studies and in situ spectroscopic analysis have provided a detailed insight into the reaction. Progress

  3. Palladium(0)​/NHC-​catalyzed reductive Heck reaction of enones: a detailed mechanistic study

    NARCIS (Netherlands)

    Raoufmoghaddam, S.; Mannathan, S.; Minnaard, A.J.; de Vries, J.G.; Reek, J.N.H.


    We have studied the mechanism of the palladium-​catalyzed reductive Heck reaction of para-​substituted enones with 4-​iodoanisole by using N,​N-​diisopropylethylamine (DIPEA) as the reductant. Kinetic studies and in situ spectroscopic anal. have provided a detailed insight into the reaction.

  4. Visible-Light Photoredox-Catalyzed Coupling Reaction of Azoles with α-Carbamoyl Sulfides. (United States)

    Jarrige, Lucie; Levitre, Guillaume; Masson, Géraldine


    A simple, straightforward strategy for the synthesis of N-substituted azoles is reported that involves a visible-light photoredox-catalyzed coupling reaction of azoles with α-carbamoyl sulfides. A variety of heterocyclic units, including pyrazoles, benzopyrazoles, benzoimidazoles, and purines, can be efficiently incorporated under mild reaction conditions in respectable yields.

  5. Unexpected Reaction Pathway for butyrylcholinesterase-catalyzed inactivation of “hunger hormone” ghrelin (United States)

    Yao, Jianzhuang; Yuan, Yaxia; Zheng, Fang; Zhan, Chang-Guo


    Extensive computational modeling and simulations have been carried out, in the present study, to uncover the fundamental reaction pathway for butyrylcholinesterase (BChE)-catalyzed hydrolysis of ghrelin, demonstrating that the acylation process of BChE-catalyzed hydrolysis of ghrelin follows an unprecedented single-step reaction pathway and the single-step acylation process is rate-determining. The free energy barrier (18.8 kcal/mol) calculated for the rate-determining step is reasonably close to the experimentally-derived free energy barrier (~19.4 kcal/mol), suggesting that the obtained mechanistic insights are reasonable. The single-step reaction pathway for the acylation is remarkably different from the well-known two-step acylation reaction pathway for numerous ester hydrolysis reactions catalyzed by a serine esterase. This is the first time demonstrating that a single-step reaction pathway is possible for an ester hydrolysis reaction catalyzed by a serine esterase and, therefore, one no longer can simply assume that the acylation process must follow the well-known two-step reaction pathway.

  6. Palladium-Catalyzed Cross-Coupling Reactions of Perfluoro Organic Compounds

    Directory of Open Access Journals (Sweden)

    Masato Ohashi


    Full Text Available In this review, we summarize our recent development of palladium(0-catalyzed cross-coupling reactions of perfluoro organic compounds with organometallic reagents. The oxidative addition of a C–F bond of tetrafluoroethylene (TFE to palladium(0 was promoted by the addition of lithium iodide, affording a trifluorovinyl palladium(II iodide. Based on this finding, the first palladium-catalyzed cross-coupling reaction of TFE with diarylzinc was developed in the presence of lithium iodide, affording α,β,β-trifluorostyrene derivatives in excellent yield. This coupling reaction was expanded to the novel Pd(0/PR3-catalyzed cross-coupling reaction of TFE with arylboronates. In this reaction, the trifluorovinyl palladium(II fluoride was a key reaction intermediate that required neither an extraneous base to enhance the reactivity of organoboronates nor a Lewis acid additive to promote the oxidative addition of a C–F bond. In addition, our strategy utilizing the synergetic effect of Pd(0 and lithium iodide could be applied to the C–F bond cleavage of unreactive hexafluorobenzene (C6F6, leading to the first Pd(0-catalyzed cross-coupling reaction of C6F6 with diarylzinc compounds.

  7. The Manganese-Catalyzed Cross-Coupling Reaction and the Influence of Trace Metals

    DEFF Research Database (Denmark)

    Santilli, Carola; Beigbaghlou, Somayyeh Sarvi; Ahlburg, Andreas


    radical as an intermediate leading to the proposal of an SRN1 pathway for the coupling. The mechanistic information gave rise to suspicion about two previously published cross-coupling reactions catalyzed by manganese(II) salts. As a result, the coupling between aryl halides and organostannanes as well......The substrate scope of the MnCl2-catalyzed cross-coupling between aryl halides and Grignard reagents has been extended to several methyl-substituted aryl iodides by performing the reaction at elevated temperature in a microwave oven. A radical clock experiment revealed the presence of an aryl...... as between aryl halides and amines were revisited. Both reactions were found impossible to reproduce without the addition of small amounts of palladium or copper and are therefore not believed to be catalyzed by manganese....

  8. Multistep enzyme catalyzed reactions for unnatural amino acids. (United States)

    D'Arrigo, Paola; Tessaro, Davide


    The use of unnatural amino acids, particularly synthetic α-amino acids, for modern drug discovery research requires the availability of enantiomerically pure isomers. Starting from a racemate, one single enantiomer can be obtained using a deracemization process. The two more common strategies of deracemization are those obtained by stereoinversion and by dynamic kinetic resolution. Both techniques will be here described using as a substrate the D,L-3-(2-naphthyl)-alanine, a non-natural amino acid: the first one employing a multi-enzymatic redox system, the second one combining an hydrolytic enzyme together with a base-catalyzed substrate racemization. In both cases, the final product, L-3-(2-naphthyl)alanine, is recovered with good yield and excellent enantiomeric excess.

  9. One enzyme, many reactions: structural basis for the various reactions catalyzed by naphthalene 1,2-dioxygenase

    Directory of Open Access Journals (Sweden)

    Daniel J. Ferraro


    Full Text Available Rieske nonheme iron oxygenases (ROs are a well studied class of enzymes. Naphthalene 1,2-dioxygenase (NDO is used as a model to study ROs. Previous work has shown how side-on binding of oxygen to the mononuclear iron provides this enzyme with the ability to catalyze stereospecific and regiospecific cis-dihydroxylation reactions. It has been well documented that ROs catalyze a variety of other reactions, including mono-oxygenation, desaturation, O- and N-dealkylation, sulfoxidation etc. NDO itself catalyzes a variety of these reactions. Structures of NDO in complex with a number of different substrates show that the orientation of the substrate in the active site controls not only the regiospecificity and stereospecificity, but also the type of reaction catalyzed. It is proposed that the mononuclear iron-activated dioxygen attacks the atoms of the substrate that are most proximal to it. The promiscuity of delivering two products (apparently by two different reactions from the same substrate can be explained by the possible binding of the substrate in slightly different orientations aided by the observed flexibility of residues in the binding pocket.

  10. Using simple donors to drive the equilibria of glycosyltransferase-catalyzed reactions. (United States)

    Gantt, Richard W; Peltier-Pain, Pauline; Cournoyer, William J; Thorson, Jon S


    We report that simple glycoside donors can drastically shift the equilibria of glycosyltransferase-catalyzed reactions, transforming NDP-sugar formation from an endothermic to an exothermic process. To demonstrate the utility of this thermodynamic adaptability, we highlight the glycosyltransferase-catalyzed synthesis of 22 sugar nucleotides from simple aromatic sugar donors, as well as the corresponding in situ formation of sugar nucleotides as a driving force in the context of glycosyltransferase-catalyzed reactions for small-molecule glycodiversification. These simple aromatic donors also enabled a general colorimetric assay for glycosyltransfer, applicable to drug discovery, protein engineering and other fundamental sugar nucleotide-dependent investigations. This study directly challenges the general notion that NDP-sugars are 'high-energy' sugar donors when taken out of their traditional biological context.

  11. Direct activation of allylic alcohols in palladium catalyzed coupling reactions

    NARCIS (Netherlands)

    Gümrükçü, Y.


    The direct use of allylic alcohols in substitution reactions without pre-activation of the hydroxyl-group into a better leaving group or the use of additional stoichiometric in situ activators remains challenging due to the poor leaving group ability of the hydroxyl-group. Hence, it is important to

  12. An Investigation of Model Catalyzed Hydrocarbon Formation Reactions

    Energy Technology Data Exchange (ETDEWEB)

    Tysoe, W. T.


    Work was focused on two areas aimed at understanding the chemistry of realistic catalytic systems: (1) The synthesis and characterization of model supported olefin metathesis catalysts. (2) Understanding the role of the carbonaceous layer present on Pd(111) single crystal model catalysts during reaction.

  13. Zinc catalyzed Guanylation reaction of Amines with Carbodiimides ...

    Indian Academy of Sciences (India)

    ... 1 and 2 under similar reaction conditions. The catalytic guanylation of N–H bonds with heterocumulenesdisplays a broad substrate scope. The amines having electron donating groups underwent higher conversionthan the amines having electron withdrawing groups to afford corresponding guanidine or urea derivatives.

  14. A simple model for chiral amplification in the aminoalcohol-catalyzed reaction of aldehydes with dialkylzinc

    Directory of Open Access Journals (Sweden)



    Full Text Available A simple explanation is offered for the recently discovered chiral amplification in the alkylation reaction of benzaldehyde by means of dialkylzinc, catalyzed by (dimethylaminoisoborneol. The model presentd is similar to, yet somewhat simpler than, the model put forward by Noyori et al.

  15. Palladium(II) Acetate Catalyzed Reductive Heck Reaction of Enones; A Practical Approach

    NARCIS (Netherlands)

    Mannathan, Subramaniyan; Raoufmoghaddam, Saeed; Reek, Joost N. H.; de Vries, Johannes G.; Minnaard, Adriaan J.


    A surprisingly practical Pd(OAc)(2) or Pd(TFA)(2)-catalyzed reductive Heck reaction between aryl iodides and alpha,beta-unsaturated ketones is described using N,N-diisopropylethylamine (DIPEA, Hunigs base) as the reductant. In general, 1 mol% of Pd(OAc)(2) is sufficient to afford good yields using

  16. Enantioselective BINOL-phosphoric acid catalyzed Pictet-Spengler reactions of N-benzyltryptamine

    NARCIS (Netherlands)

    Sewgobind, N.V.; Wanner, M.J.; Ingemann, S.; de Gelder, R.; van Maarseveen, J.H.; Hiemstra, H.


    Optically active tetrahydro-beta-carbolines were synthesized via an (R)-BINOL-phosphoric acid-catalyzed asynunetric Pictet-Spengler reaction of N-benzyltryptamine with a series of aromatic and aliphatic aldehydes. The tetrahydro-beta-carbolines were obtained in yields ranging from 77% to 97% and

  17. Palladium(II) acetate catalyzed reductive Heck reaction of enones: a practical approach

    NARCIS (Netherlands)

    Mannathan, S.; Raoufmoghaddam, S.; Reek, J.N.H.; de Vries, J.G.; Minnaard, A.J.


    A surprisingly practical Pd(OAc)​2 or Pd(TFA)​2-​catalyzed reductive Heck reaction between aryl iodides and α,​β-​unsatd. ketones is described using N,​N-​diisopropylethylamine (DIPEA, Huenigs base) as the reductant. In general, 1 mol % of Pd(OAc)​2 is sufficient to afford good yields using

  18. Silver-Catalyzed Synthesis of Diaryl Selenides by Reaction of Diaryl Diselenides with Aryl Boronic Acids. (United States)

    Goldani, Bruna; Ricordi, Vanessa G; Seus, Natália; Lenardão, Eder J; Schumacher, Ricardo F; Alves, Diego


    We described herein our results on the silver-catalyzed synthesis of diaryl selenides via a cross-coupling reaction of diaryl diselenides with aryl boronic acids. The methodology is tolerant to electron-donor and electron-withdrawing groups at the substrates and the desired products were obtained in good to excellent yields.

  19. Probing the mechanism of 1,4-conjugate elimination reactions catalyzed by terpene synthases. (United States)

    Faraldos, Juan A; Gonzalez, Veronica; Li, Amang; Yu, Fanglei; Köksal, Mustafa; Christianson, David W; Allemann, Rudolf K


    The reaction mechanisms of (E)-β-farnesene synthase (EBFS) and isoprene synthase (ISPS), enzymes that catalyze a formal regiospecific 1,4-conjugate elimination of hydrogen diphosphate from (E,E)-farnesyl and dimethylallyl diphosphate (FDP and DMADP) to generate the semiochemicals (E)-β-farnesene and isoprene, respectively, were probed with substrate analogs and kinetic measurements. The results support stepwise reaction mechanisms through analogous enzyme-bound allylic cationic intermediates. For EBFS, we demonstrate that the elimination reaction can proceed via the enzyme-bound intermediate trans-nerolidyl diphosphate, while for ISPS the intermediacy of 2-methylbut-3-enyl 2-diphosphate can be inferred from the product outcome when deuterated DMADPs are used as substrates. Possible implications derived from the mechanistic details of the EBFS-catalyzed reaction for the evolution of sesquiterpene synthases are discussed.

  20. Copper-catalyzed selective hydroamination reactions of alkynes


    Shi, Shi-Liang; Buchwald, Stephen L.


    The development of selective reactions that utilize easily available and abundant precursors for the efficient synthesis of amines is a longstanding goal of chemical research. Despite the centrality of amines in a number of important research areas, including medicinal chemistry, total synthesis and materials science, a general, selective, and step-efficient synthesis of amines is still needed. In this work we describe a set of mild catalytic conditions utilizing a single copper-based catalys...

  1. Investigation of confinement effects on zeolite-catalyzed methylation reactions


    Van der Mynsbrugge, Jeroen; De Wispelaere, Kristof; Ridder, Jeroen de; Hemelsoet, Karen; Waroquier, Michel; Van Speybroeck, Veronique


    Catalytic conversion of methanol to light olefins (MTO) over acidic zeolites is currently one of the most prominent alternatives to traditional crude oil cracking processes for the production of ethene and propene. The underlying reaction mechanisms have been under debate for decades, with current insight strongly supporting an indirect mechanism based on the hydrocarbon pool hypothesis: olefin formation is found to occur through repeated methylation and subsequent elimination and/or cracking...

  2. Probing the Mechanism of 1,4-Conjugate Elimination Reactions Catalyzed by Terpene Synthases


    Faraldos, Juan A.; Gonzalez, Veronica; Li, Amang; Yu, Fanglei; Köksal, Mustafa; Christianson, David W.; Allemann, Rudolf K.


    The reaction mechanisms of (E)-β-farnesene synthase (EBFS) and isoprene synthase (ISPS), enzymes that catalyze a formal regioespecific 1,4-conjugate elimination of hydrogen-diphosphate from (E, E)-farnesyl and dimethylallyl diphosphate (FDP and DMADP) to generate the semiochemicals (E)-β-farnesene and isoprene, respectively, were probed with substrate analogs and kinetic measurements. The results support stepwise reaction mechanisms through analogous enzyme-bound allylic cationic intermediate...

  3. Advances in Metal-Catalyzed Cross-Coupling Reactions of Halogenated Quinazolinones and Their Quinazoline Derivatives

    Directory of Open Access Journals (Sweden)

    Malose Jack Mphahlele


    Full Text Available Halogenated quinazolinones and quinazolines are versatile synthetic intermediates for the metal-catalyzed carbon–carbon bond formation reactions such as the Kumada, Stille, Negishi, Sonogashira, Suzuki-Miyaura and Heck cross-coupling reactions or carbon-heteroatom bond formation via the Buchwald-Hartwig cross-coupling to yield novel polysubstituted derivatives. This review presents an overview of the application of these methods on halogenated quinazolin-4-ones and their quinazolines to generate novel polysubstituted derivatives.

  4. Palladium-catalyzed cross-coupling reactions of aryl boronic acids with aryl halides in water. (United States)

    Wang, Shaoyan; Zhang, Zhiqiang; Hu, Zhizhi; Wang, Yue; Lei, Peng; Chi, Haijun


    An efficient Suzuki cross-coupling reaction using a variety of aryl halides in neat water was developed. The Pd-catalyzed reaction between aryl bromides or chlorides and phenyl boronic acids was compatible with various functional groups and affords biphenyls in good to excellent yields without requirement of organic cosolvents. The air stability and solubility in water of the palladium-phosphinous acid complexes were considered to facilitate operation of the coupling reaction and product isolation. The reaction conditions including Pd catalyst selection, temperature, base and catalyst recoverability were also investigated.

  5. The three transglycosylation reactions catalyzed by cyclodextrin glycosyltransferase from Bacillus circulans (strain 251) proceed via different kinetic mechanisms

    NARCIS (Netherlands)

    Veen, Bart A. van der; Alebeek, Gert-Jan W.M. van; Uitdehaag, Joost C.M.; Dijkstra, Bauke W.; Dijkhuizen, Lubbert

    Cyclodextrin glycosyltransferase (CGTase) catalyzes three transglycosylation reactions via a double displacement mechanism involving a covalent enzyme-intermediate complex (substituted-enzyme intermediate). Characterization of the three transglycosylation reactions, however, revealed that they

  6. Pentanidium-catalyzed enantioselective phase-transfer conjugate addition reactions

    KAUST Repository

    Ma, Ting


    A new chiral entity, pentanidium, has been shown to be an excellent chiral phase-transfer catalyst. The enantioselective Michael addition reactions of tert-butyl glycinate-benzophenone Schiff base with various α,β- unsaturated acceptors provide adducts with high enantioselectivities. A successful gram-scale experiment at a low catalyst loading of 0.05 mol % indicates the potential for practical applications of this methodology. Phosphoglycine ester analogues can also be utilized as the Michael donor, affording enantioenriched α-aminophosphonic acid derivatives and phosphonic analogues of (S)-proline. © 2011 American Chemical Society.

  7. Enhanced Diffusion of Enzymes that Catalyze Exothermic Reactions. (United States)

    Golestanian, Ramin


    Enzymes have been recently found to exhibit enhanced diffusion due to their catalytic activities. A recent experiment [C. Riedel et al., Nature (London) 517, 227 (2015)] has found evidence that suggests this phenomenon might be controlled by the degree of exothermicity of the catalytic reaction involved. Four mechanisms that can lead to this effect, namely, self-thermophoresis, boost in kinetic energy, stochastic swimming, and collective heating are critically discussed, and it is shown that only the last two can be strong enough to account for the observations. The resulting quantitative description is used to examine the biological significance of the effect.

  8. Enantioselective Henry reaction catalyzed by "ship in a bottle" complexes. (United States)

    Bania, Kusum K; Karunakar, Galla V; Goutham, Kommuru; Deka, Ramesh C


    Two chiral Schiff-base complexes of copper(II) have been successfully encapsulated inside the cavity of zeolite-NaY via a "ship in a bottle" synthesis method. The presence of the two complexes inside the cages of zeolite-Y has been confirmed based on various spectrochemical and physicochemical techniques, viz. FTIR, UV-vis/DRS, ESR, XPS, CV, EDX, SEM, and TGA. Zeolite-encapsulated chiral copper(II) Schiff-base complexes are found to give a high-enantioselective (84% ee, R conformation) nitro-aldol product at -20 °C. The encapsulated copper complexes are found to show higher catalytic efficiency than their homogeneous counterparts under identical conditions. Density functional theory (DFT) calculation has been implemented to understand the effect of the zeolite matrix on structural, electronic, and reactivity properties of the synthesized complexes. Theoretical calculation predicts that upon encapsulation into the zeolite matrix the Cu center becomes more susceptible to nucleophilic attack, favoring a nitro-aldol reaction. A plausible mechanism is suggested based on the experimental and theoretical results. The structures of reaction intermediates and transition state(s) involved in the catalytic cycle are derived using DFT.

  9. Mutagenicity screening of reaction products from the enzyme-catalyzed oxidation of phenolic pollutants

    Energy Technology Data Exchange (ETDEWEB)

    Massey, I.J.; Aitken, M.D.; Ball, L.M.; Heck, P.E. (Univ. of North Carolina, Chapel Hill, NC (United States). Dept. of Environmental Sciences and Engineering)


    Phenol-oxidizing enzymes such as peroxidases, laccases, and mushroom polyphenol oxidase are capable of catalyzing the oxidation of a wide range of phenolic pollutants. Although the use of these enzymes in waste-treatment applications has been proposed by a number of investigators, little information exists on the toxicological characteristics of the oxidation products. The enzymes chloroperoxidase, horseradish peroxidase, lignin peroxidase, and mushroom polyphenol oxidase were used in this study to catalyze the oxidation of phenol, several mono-substituted phenols, and pentachlorophenol. Seventeen reaction mixtures representing selected combinations of enzyme and parent phenol were subjected to mutagenicity screening using the Ames Salmonella typhimurium plate incorporation assay; five selected mixtures were also incubated with the S9 microsomal preparation to detect the possible presence of promutagens. The majority of reaction mixtures tested were not directly mutagenic, and none of those tested with S9 gave a positive response. Such lack of mutagenicity of enzymatic oxidation products provides encouragement for establishing the feasibility of enzyme-catalyzed oxidation as a waste-treatment process. The only positive responses were obtained with reaction products from the lignin peroxidase-catalyzed oxidation of 2-nitrophenol and 4-nitrophenol. Clear positive responses were observed when strain TA100 was incubated with 2-nitrophenol reaction-product mixtures, and when strain TA98 was incubated with the 4-nitrophenol reaction mixture. Additionally, 2,4-dinitrophenol was identified as a reaction product from 4-nitrophenol, and preliminary evidence indicates that both 2,4- and 2,6-dinitrophenol are produced from the oxidation of 2-nitrophenol. Possible mechanism by which these nitration reactions occur are discussed.

  10. Copper-catalyzed selective hydroamination reactions of alkynes (United States)

    Shi, Shi-Liang; Buchwald, Stephen L.


    The development of selective reactions that utilize easily available and abundant precursors for the efficient synthesis of amines is a longstanding goal of chemical research. Despite the centrality of amines in a number of important research areas, including medicinal chemistry, total synthesis and materials science, a general, selective, and step-efficient synthesis of amines is still needed. In this work we describe a set of mild catalytic conditions utilizing a single copper-based catalyst that enables the direct preparation of three distinct and important amine classes (enamines, α-chiral branched alkylamines, and linear alkylamines) from readily available alkyne starting materials with high levels of chemo-, regio-, and stereoselectivity. This methodology was applied to the asymmetric synthesis of rivastigmine and the formal synthesis of several other pharmaceutical agents, including duloxetine, atomoxetine, fluoxetine, and tolterodine. PMID:25515888

  11. Applications of Palladium-Catalyzed C–N Cross-Coupling Reactions (United States)


    Pd-catalyzed cross-coupling reactions that form C–N bonds have become useful methods to synthesize anilines and aniline derivatives, an important class of compounds throughout chemical research. A key factor in the widespread adoption of these methods has been the continued development of reliable and versatile catalysts that function under operationally simple, user-friendly conditions. This review provides an overview of Pd-catalyzed N-arylation reactions found in both basic and applied chemical research from 2008 to the present. Selected examples of C–N cross-coupling reactions between nine classes of nitrogen-based coupling partners and (pseudo)aryl halides are described for the synthesis of heterocycles, medicinally relevant compounds, natural products, organic materials, and catalysts. PMID:27689804

  12. Development of Fluorous Lewis Acid-Catalyzed Reactions

    Directory of Open Access Journals (Sweden)

    Joji Nishikido


    Full Text Available Organic synthetic methodology in the 21st century aims to conform to the principles of green sustainable chemistry (GSC and we may expect that in the future, the realization of GSC will be an important objective for chemical industries. An important aim of synthetic organic chemistry is to implement waste-free and environmentally-benign industrial processes using Lewis acids as versatile as aluminum choride. A key technological objective of our work in this area has been to achieve a “catalyst recycling system that utilizes the high activity and structural features of fluorous Lewis acid catalysts”. Thus, we have developed a series of novel fluorous Lewis acid catalysts, namely the ytterbium(III, scandium(III, tin(IV or hafnium(IV bis(perfluoroalkanesulfonylamides or tris(perfluoro- alkanesulfonylmethides. Our catalysts are recyclable and effective for acylations of alcohols and aromatics, Baeyer-Villiger reactions, direct esterifications and transesterifications in a fluorous biphasic system (FBS, in supercritical carbon dioxide and on fluorous silica gel supports.

  13. The role of vanadium haloperoxidases in the formation of volatile brominated compounds and their impact on the environment. (United States)

    Wever, Ron; van der Horst, Michael A


    Vanadium haloperoxidases differ strongly from heme peroxidases in substrate specificity and stability and in contrast to a heme group they contain the bare metal oxide vanadate as a prosthetic group. These enzymes specifically oxidize halides in the presence of hydrogen peroxide into hypohalous acids. These reactive halogen intermediates will react rapidly and aspecifically with many organic molecules. Marine algae and diatoms containing these iodo- and bromoperoxidases produce short-lived brominated methanes (bromoform, CHBr3 and dibromomethane CH2Br2) or iodinated compounds. Some seas and oceans are supersaturated with these compounds and they form an important source of bromine to the troposphere and lower stratosphere and contribute significantly to the global budget of halogenated hydrocarbons. This perspective focuses, in particular, on the biosynthesis of these volatile compounds and the direct or indirect involvement of vanadium haloperoxidases in the production of huge amounts of bromoform and dibromomethane. Some of the global sources are discussed and from the literature a picture emerges in which oxidized brominated species generated by phytoplankton, seaweeds and cyanobacteria react with dissolved organic matter in seawater, resulting in the formation of intermediate brominated compounds. These compounds are unstable and decay via a haloform reaction to form an array of volatile brominated compounds of which bromoform is the major component followed by dibromomethane.

  14. Palladium-catalyzed ring-opening reactions of cyclopropanated 7-oxabenzonorbornadiene with alcohols

    Directory of Open Access Journals (Sweden)

    Katrina Tait


    Full Text Available Palladium-catalyzed ring-opening reactions of cyclopropanated 7-oxabenzonorbornadiene derivatives using alcohol nucleophiles were investigated. The optimal conditions were found to be 10 mol % PdCl2(CH3CN2 in methanol, offering yields up to 92%. The reaction was successful using primary, secondary and tertiary alcohol nucleophiles and was compatible with a variety of substituents on cyclopropanated oxabenzonorbornadiene. With unsymmetrical C1-substituted cyclopropanated 7-oxabenzonorbornadienes, the regioselectivity of the reaction was excellent, forming only one regioisomer in all cases.

  15. Ruthenium-Catalyzed Synthesis of 1,5-Dichlorides by Sequential Intermolecular Kharasch Reactions


    Thommes, Katrin; Fernandez-Zumel, Mariano Alfonso; Buron, Charlotte; Godinat, Aurélien; Scopelliti, Rosario; Severin, Kay


    Sequential intermolecular atom transfer radical addition reactions of activated dichlorides Cl2CRR′ (R = CN, CO2Et, R′ = H, CN, CO2Et) with two olefins catalyzed by [Cp*RuCl2(PPh3)] in the presence Mg allow the synthesis of linear 1,5-dichlorides. Different olefins can be employed in the first and in the second addition reaction. The reaction products are interesting synthetic precursors as demonstrated by the synthesis of two cyclopentanes by Mg-induced dechlorination. The structure of trans...

  16. The role of hydrogen bonding in the enzymatic reaction catalyzed by HIV-1 protease


    Trylska, Joanna; Grochowski, Paweł; McCammon, J. Andrew


    The hydrogen-bond network in various stages of the enzymatic reaction catalyzed by HIV-1 protease was studied through quantum-classical molecular dynamics simulations. The approximate valence bond method was applied to the active site atoms participating directly in the rearrangement of chemical bonds. The rest of the protein with explicit solvent was treated with a classical molecular mechanics model. Two possible mechanisms were studied, general-acid/general-base (GA/GB) with Asp 25 protona...

  17. Polycyclization Enabled by Relay Catalysis: One-Pot Manganese-Catalyzed C-H Allylation and Silver-Catalyzed Povarov Reaction. (United States)

    Chen, Shi-Yong; Li, Qingjiang; Liu, Xu-Ge; Wu, Jia-Qiang; Zhang, Shang-Shi; Wang, Honggen


    In this study, a Mn I /Ag I -based relay catalysis process is described for the one-pot synthesis of polycyclic products by a formal [3+2] and [4+2] cycloaddition reaction cascade. A manganese(I) complex catalyzed the first example of directed C-H allylation with allenes, setting the stage for an in situ Povarov cyclization catalyzed by silver(I). The reaction proceeds with high bond-forming efficiency (three C-C bonds), broad substrate scope, high regio- and stereoselectivity, and 100 % atom economy. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Origins of Enantioselectivity during Allylic Substitution Reactions Catalyzed by Metallacyclic Iridium Complexes (United States)

    Madrahimov, Sherzod T.; Hartwig, John F.


    In depth mechanistic studies of iridium catalyzed regioselective and enantioselective allylic substitution reactions are presented. A series of cyclometallated allyliridium complexes that are kinetically and chemically competent to be intermediates in the allylic substitution reactions was prepared and characterized by 1D and 2D NMR spectroscopies and solid state structural analysis. The rates of epimerization of the less thermodynamically stable diastereomeric allyliridium complexes to the thermodynamically more stable allyliridium stereoisomers were measured. The rates of nucleophilic attack by aniline and by N-methylaniline on the isolated allyliridium complexes were also measured. Attack on the thermodynamically less stable allyliridium complex was found to be orders of magnitude faster than attack on the thermodynamically more stable complex, yet the major enantiomer of the catalytic reaction is formed from the more stable diastereomer. Comparison of the rates of nucleophilic attack to the rates of epimerization of the diastereomeric allyliridium complexes containing a weakly-coordinating counterion showed that nucleophilic attack on the less stable allyliridium species is much faster than conversion of the less stable isomer to the more stable isomer. These observations imply that Curtin-Hammett conditions are not met during iridium catalyzed allylic substitution reactions by η3-η1-η3 interconversion. Rather, these data imply that when these conditions exist for this reaction, they are created by reversible oxidative addition and the high selectivity of this oxidative addition step to form the more stable diastereomeric allyl complex leads to the high enantioselectivity. The stereochemical outcome of the individual steps of allylic substitution was assessed by reaction of deuterium-labeled substrates. The reaction was shown to occur by oxidative addition with inversion of configuration, followed by an outer sphere nucleophilic attack that leads to a second

  19. Au(I/Au(III-catalyzed Sonogashira-type reactions of functionalized terminal alkynes with arylboronic acids under mild conditions

    Directory of Open Access Journals (Sweden)

    Deyun Qian


    Full Text Available A straightforward, efficient, and reliable redox catalyst system for the Au(I/Au(III-catalyzed Sonogashira cross-coupling reaction of functionalized terminal alkynes with arylboronic acids under mild conditions has been developed.

  20. Yttrium (III chloride catalyzed Mannich reaction: An efficient procedure for the synthesis of β-amino carbonyl compounds

    Directory of Open Access Journals (Sweden)

    Venkateswarlu Yekkirala


    Full Text Available Yttrium (III chloride catalyzed Mannich reaction of aldehydes with ketones and amines in acetonitrile at reflux temperature to give various β-amino carbonyl compounds in very good yields.

  1. Keratin Protein-Catalyzed Nitroaldol (Henry) Reaction and Comparison with Other Biopolymers. (United States)

    Häring, Marleen; Pettignano, Asja; Quignard, Françoise; Tanchoux, Nathalie; Díaz Díaz, David


    Here we describe a preliminary investigation on the ability of natural keratin to catalyze the nitroaldol (Henry) reaction between aldehydes and nitroalkanes. Both aromatic and heteroaromatic aldehydes bearing strong or moderate electron-withdrawing groups were converted into the corresponding β-nitroalcohol products in both DMSO and in water in the presence of tetrabutylammonium bromide (TBAB) as a phase transfer catalyst. Negligible background reactions (i.e., negative control experiment in the absence of keratin protein) were observed in these solvent systems. Aromatic aldehydes bearing electron-donating groups and aliphatic aldehydes showed poor or no conversion, respectively. In general, the reactions in water/TBAB required twice the amount of time than in DMSO to achieve similar conversions. Moreover, comparison of the kinetics of the keratin-mediated nitroaldol (Henry) reaction with other biopolymers revealed slower rates for the former and the possibility of fine-tuning the kinetics by appropriate selection of the biopolymer and solvent.

  2. Keratin Protein-Catalyzed Nitroaldol (Henry Reaction and Comparison with Other Biopolymers

    Directory of Open Access Journals (Sweden)

    Marleen Häring


    Full Text Available Here we describe a preliminary investigation on the ability of natural keratin to catalyze the nitroaldol (Henry reaction between aldehydes and nitroalkanes. Both aromatic and heteroaromatic aldehydes bearing strong or moderate electron-withdrawing groups were converted into the corresponding β-nitroalcohol products in both DMSO and in water in the presence of tetrabutylammonium bromide (TBAB as a phase transfer catalyst. Negligible background reactions (i.e., negative control experiment in the absence of keratin protein were observed in these solvent systems. Aromatic aldehydes bearing electron-donating groups and aliphatic aldehydes showed poor or no conversion, respectively. In general, the reactions in water/TBAB required twice the amount of time than in DMSO to achieve similar conversions. Moreover, comparison of the kinetics of the keratin-mediated nitroaldol (Henry reaction with other biopolymers revealed slower rates for the former and the possibility of fine-tuning the kinetics by appropriate selection of the biopolymer and solvent.

  3. Transition Metal Catalyzed Reactions for Forming Carbon–Oxygen and Carbon–Carbon Bonds

    DEFF Research Database (Denmark)

    Sølvhøj, Amanda Birgitte

    Dehydrogenative ester formation with a ruthenium NHC complex A new atom-economical methodology for synthesizing esters by the dehydrogenative coupling of primary alcohols was developed. The reaction is catalyzed by the ruthenium N-heterocyclic carbene complex RuCl2(IiPr)(p-cymene). By screening...... the effect of different additives, solvents and loadings on the selfcondensation of pentanol, the optimal reaction conditions were found to be 2.5 mol % of RuCl2(IiPr)(p-cymene), 4.5 mol % of PCy3 and 10 mol % of KOH in refluxing mesitylene, which gave the ester in nearly quantitative yield by GC analysis...... could be used as substrates, but the yields were generally poor due to decarbonylation of the substrate as a considerable side reaction. Some preliminary mechanistic investigations were performed. The results of these confirmed that the reaction is indeed dehydrogenative with the liberation of two moles...

  4. Ni- or Cu-catalyzed cross-coupling reaction of alkyl fluorides with Grignard reagents. (United States)

    Terao, Jun; Ikumi, Aki; Kuniyasu, Hitoshi; Kambe, Nobuaki


    n-Octyl fluoride underwent a cross-coupling reaction with n-propylmagnesium bromide in the presence of 1,3-butadiene using NiCl2 as a catalyst at room temperature to give undecane in moderate yields. This alkyl-alkyl cross-coupling proceeded more efficiently when CuCl2 was employed instead of NiCl2. Addition of 1,3-butadiene dramatically improved the yields of the coupling products from primary alkyl Grignard reagents in both Ni- and Cu-catalyzed reactions. Alkyl fluorides efficiently reacted with tertiary alkyl and phenyl Grignard reagents using CuCl2 in the absence of 1,3-butadiene to afford the coupling products in high yields. The competitive reaction of a mixture of alkyl halides (R-X; X = F, Cl, Br) with nC5H11MgBr showed that the reactivities of the halides increase in the order R-Cl R-F R-Br. In contrast, in the Cu-catalyzed reaction with PhMgBr, the reactivities increase in the order R-Cl R-Br R-F.

  5. Sulfuric, hydrochloric, and nitric acid-catalyzed triacetone triperoxide (TATP) reaction mixtures: an aging study. (United States)

    Fitzgerald, Mark; Bilusich, Daniel


    The organic peroxide explosive triacetone triperoxide (TATP) is regularly encountered by law enforcement agents in various stages of its production. This study utilizes solid-phase microextraction (SPME) and gas chromatography/mass spectrometry (GC/MS) to examine sulfuric acid-, hydrochloric acid-, and nitric acid-catalyzed TATP syntheses during the initial 24 h of these reactions at low temperatures (5-9°C). Additionally, aging of the reaction mixtures was examined at both low and ambient temperatures (19-21°C) for a further 9 days. For each experiment, TATP could be readily identified in the headspace above the reaction mixture 1 h subsequent to the combination of reagents; at 24 h, TATP and diacetone diperoxide (DADP) were prominent. TATP degraded more rapidly than DADP. Additionally, chlorinated acetones chloroacetone and 1,1,-dichloroacetone were identified in the headspace above the hydrochloric acid-catalyzed TATP reaction mixture. These were not present when the catalyst was sulfuric acid or nitric acid. 2011 American Academy of Forensic Sciences. Published 2011. This article is a U.S. Government work and is in the public domain in the U.S.A.

  6. Practical synthesis of 1,3-oleoyl 2-docosahexaenoylglycerol by lipase-catalyzed reactions: An evaluation of different reaction routes

    DEFF Research Database (Denmark)

    Zhang, Hong; Onal, G.; Wijesundera, C.


    Three new synthetic routes were critically evaluated for the lipase-catalyzed production of 1,3-oleoyl-2 docosahexaenoylglycerol (ODD) in relatively large-scale (approximately 200 g). First, the production of 1,3-diolein by the reaction of glycerol and oleic acid followed by incorporation...... of docosahexaenoic (DHA) ethyl ester at the sn-2 position was studied. 1,3-Diolein was produced in 68.3% and 84.6% yield when stoichiometric amounts of the Substrates were reacted at 25 degrees C for 8 h in the presence of 10% Novozym 435 and Lipozyme RM IM, respectively. Further increase in reaction temperature...... and time led to decrease in the 1,3-diolein yield. However, only a 9.4% yield of triacylglycerol was obtained in the subsequent reaction step when the 1,3-diolein was reacted with DHA ethyl ester in the presence of Novozym 435. Secondly, the feasibility of direct acidolysis was studied. Acidolysis...

  7. Precision Synthesis of Functional Polysaccharide Materials by Phosphorylase-Catalyzed Enzymatic Reactions

    Directory of Open Access Journals (Sweden)

    Jun-ichi Kadokawa


    Full Text Available In this review article, the precise synthesis of functional polysaccharide materials using phosphorylase-catalyzed enzymatic reactions is presented. This particular enzymatic approach has been identified as a powerful tool in preparing well-defined polysaccharide materials. Phosphorylase is an enzyme that has been employed in the synthesis of pure amylose with a precisely controlled structure. Similarly, using a phosphorylase-catalyzed enzymatic polymerization, the chemoenzymatic synthesis of amylose-grafted heteropolysaccharides containing different main-chain polysaccharide structures (e.g., chitin/chitosan, cellulose, alginate, xanthan gum, and carboxymethyl cellulose was achieved. Amylose-based block, star, and branched polymeric materials have also been prepared using this enzymatic polymerization. Since phosphorylase shows a loose specificity for the recognition of substrates, different sugar residues have been introduced to the non-reducing ends of maltooligosaccharides by phosphorylase-catalyzed glycosylations using analog substrates such as α-d-glucuronic acid and α-d-glucosamine 1-phosphates. By means of such reactions, an amphoteric glycogen and its corresponding hydrogel were successfully prepared. Thermostable phosphorylase was able to tolerate a greater variance in the substrate structures with respect to recognition than potato phosphorylase, and as a result, the enzymatic polymerization of α-d-glucosamine 1-phosphate to produce a chitosan stereoisomer was carried out using this enzyme catalyst, which was then subsequently converted to the chitin stereoisomer by N-acetylation. Amylose supramolecular inclusion complexes with polymeric guests were obtained when the phosphorylase-catalyzed enzymatic polymerization was conducted in the presence of the guest polymers. Since the structure of this polymeric system is similar to the way that a plant vine twines around a rod, this polymerization system has been named

  8. Asymmetric Brønsted acid-catalyzed aza-Diels–Alder reaction of cyclic C-acylimines with cyclopentadiene

    Directory of Open Access Journals (Sweden)

    Magnus Rueping


    Full Text Available A new chiral Brønsted acid-catalyzed aza-Diels–Alder reaction of cyclic C-acylimines with cyclopentadiene has been developed. The reaction provides optically active aza-tetracycles in good yields with high diastereo- and enantioselectivities under mild reaction conditions.

  9. Modeling the Reactions Catalyzed by Coenzyme B12 Dependent Enzymes: Accuracy and Cost-Quality Balance. (United States)

    Wick, Christian R; Smith, David M


    The reactions catalyzed by coenzyme B12 dependent enzymes are formally initiated by the homolytic cleavage of a carbon-cobalt bond and a subsequent or concerted H-atom-transfer reaction. A reasonable model chemistry for describing those reactions should, therefore, account for an accurate description of both reactions. The inherent limitation due to the necessary system size renders the coenzyme B12 system a suitable candidate for DFT or hybrid QM/MM methods; however, the accurate description of both homolytic Co-C cleavage and H-atom-transfer reactions within this framework is challenging and can lead to controversial results with varying accuracy. We present an assessment study of 16 common density functionals applied to prototypical model systems for both reactions. H-abstraction reactions were modeled on the basis of four reference reactions designed to resemble a broad range of coenzyme B12 reactions. The Co-C cleavage reaction is treated by an ONIOM(QM/MM) setup that is in excellent agreement with solution-phase experimental data and is as accurate as full DFT calculations on the complete model system. We find that the meta-GGAs TPSS-D3 and M06L-D3 and the meta-hybrid M06-D3 give the best overall performance with MUEs for both types of reactions below 10 kJ mol-1. Our recommended model chemistry allows for a fast and accurate description of coenzyme B12 chemistry that is readily applicable to study the reactions in an enzymatic framework.

  10. Palladium-atom catalyzed formic acid decomposition and the switch of reaction mechanism with temperature. (United States)

    He, Nan; Li, Zhen Hua


    Formic acid decomposition (FAD) reaction has been an innovative way for hydrogen energy. Noble metal catalysts, especially palladium-containing nanoparticles, supported or unsupported, perform well in this reaction. Herein, we considered the simplest model, wherein one Pd atom is used as the FAD catalyst. With high-level theoretical calculations of CCSD(T)/CBS quality, we investigated all possible FAD pathways. The results show that FAD catalyzed by one Pd atom follows a different mechanism compared with that catalyzed by surfaces or larger clusters. At the initial stage of the reaction, FAD follows a dehydration route and is quickly poisoned by CO due to the formation of very stable PdCO. PdCO then becomes the actual catalyst for FAD at temperatures approximately below 1050 K. Beyond 1050 K, there is a switch of catalyst from PdCO to Pd atom. The results also show that dehydration is always favoured over dehydrogenation on either the Pd-atom or PdCO catalyst. On the Pd-atom catalyst, neither dehydrogenation nor dehydration follows the formate mechanism. In contrast, on the PdCO catalyst, dehydrogenation follows the formate mechanism, whereas dehydration does not. We also systematically investigated the performance of 24 density functional theory methods. We found that the performance of the double hybrid mPW2PLYP functional is the best, followed by the B3LYP, B3PW91, N12SX, M11, and B2PLYP functionals.

  11. In situ Regeneration of NADH via Lipoamide Dehydrogenase-catalyzed Electron Transfer Reaction Evidenced by Spectroelectrochemistry

    Energy Technology Data Exchange (ETDEWEB)

    Tam, Tsz Kin; Chen, Baowei; Lei, Chenghong; Liu, Jun


    NAD/NADH is a coenzyme found in all living cells, carrying electrons from one reaction to another. We report on characterizations of in situ regeneration of NADH via lipoamide dehydrogenase (LD)-catalyzed electron transfer reaction to regenerate NADH using UV-vis spectroelectrochemistry. The Michaelis-Menten constant (Km) and maximum velocity (Vmax) of NADH regeneration were measured as 0.80 {+-} 0.15 mM and 1.91 {+-} 0.09 {micro}M s-1 in a 1-mm thin-layer spectroelectrochemical cell using gold gauze as the working electrode at the applied potential -0.75 V (vs. Ag/AgCl). The electrocatalytic reduction of the NAD system was further coupled with the enzymatic conversion of pyruvate to lactate by lactate dehydrogenase to examine the coenzymatic activity of the regenerated NADH. Although the reproducible electrocatalytic reduction of NAD into NADH is known to be difficult compared to the electrocatalytic oxidation of NADH, our spectroelectrochemical results indicate that the in situ regeneration of NADH via LD-catalyzed electron transfer reaction is fast and sustainable and can be potentially applied to many NAD/NADH-dependent enzyme systems.

  12. Role of Diffusion in the Kinetics of Reversible Enzyme-catalyzed Reactions

    Energy Technology Data Exchange (ETDEWEB)

    Szabo, Attila [National Institute of Digestive and Kidney Diseases, Maryland (United States); Zhou, Huan Xiang [Florida State University, Florida (United States)


    The accurate expression for the steady-state velocity of an irreversible enzyme-catalyzed reaction obtained by Shin and co-workers (J. Chem. Phys. 2001, 115, 1455) is generalized to allow for the rebinding of the product. The amplitude of the power-law (t{sup -1/2}) relaxation of the free- and bound-enzyme concentrations to steady-state values is expressed in terms of the steady-state velocity and the intrinsic (chemical) rate constants. This result is conjectured to be exact, even though our expression for the steady-state velocity in terms of microscopic parameters is only approximate

  13. Cure reaction of epoxy resins catalyzed by graphite-based nanofiller (United States)

    Corcione, C. Esposito; Acocella, Maria Rosaria; Giuri, Antonella; Maffezzoli, Alfonso; Guerra, Gaetano


    A significant effort was directed to the synthesis of graphene stacks/epoxy nanocomposites and to the analysis of the effect of a graphene precursor on cure reaction of a model epoxy matrix. A comparative thermal analysis of epoxy resins filled with an exfoliated graphite oxide eGO were conducted. The main aim was to understand the molecular origin of the influence of eGO on the Tg of epoxy resins. The higher Tg values previously observed for low curing temperatures, for epoxy resins with graphite-based nanofillers, were easily rationalized by a catalytic activity of graphitic layers on the reaction between the epoxy and amine groups of the resin, which leads to higher crosslinking density in milder conditions. A kinetic analysis of the cure mechanism of the epoxy resin associated to the catalytical activity of the graphite based filler was performed by isothermal DSC measurements. The DSC results showed that the addition of graphite based filler greatly increased the enthalpy of epoxy reaction and the reaction rate, confirming the presence of a catalytic activity of graphitic layers on the crosslinking reaction between the epoxy resin components (epoxide oligomer and di-amine). A kinetic modelling analysis, arising from an auto-catalyzed reaction mechanism, was finally applied to isothermal DSC data, in order to predict the cure mechanism of the epoxy resin in presence of the graphite based nanofiller.

  14. Mechanistic Implications for the Ni(I-Catalyzed Kumada Cross-Coupling Reaction

    Directory of Open Access Journals (Sweden)

    Linda Iffland


    Full Text Available Herein we report on the cross-coupling reaction of phenylmagnesium bromide with aryl halides using the well-defined tetrahedral Ni(I complex, [(TriphosNiICl] (Triphos = 1,1,1-tris(diphenylphosphinomethylethane. In the presence of 0.5 mol % [(TriphosNiICl], good to excellent yields (75–97% of the respective coupling products within a reaction time of only 2.5 h at room temperature were achieved. Likewise, the tripodal Ni(IIcomplexes [(κ2-TriphosNiIICl2] and [(κ3-TriphosNiIICl](X (X = ClO4, BF4 were tested as potential pre-catalysts for the Kumada cross-coupling reaction. While the Ni(II complexes also afford the coupling products in comparable yields, mechanistic investigations by UV/Vis and electron paramagnetic resonance (EPR spectroscopy indicate a Ni(I intermediate as the catalytically active species in the Kumada cross-coupling reaction. Based on experimental findings and density functional theory (DFT calculations, a plausible Ni(I-catalyzed reaction mechanism for the Kumada cross-coupling reaction is presented.

  15. The Palladium-Catalyzed Aerobic Kinetic Resolution of Secondary Alcohols: Reaction Development, Scope, and Applications

    KAUST Repository

    Ebner, Davidâ C.


    The first palladium-catalyzed enantioselective oxidation of secondary alcohols has been developed, utilizing the readily available diamine (-)-sparteine as a chiral ligand and molecular oxygen as the stoichiometric oxidant. Mechanistic insights regarding the role of the base and hydrogen-bond donors have resulted in several improvements to the original system. Namely, addition of cesium carbonate and tert-butyl alcohol greatly enhances reaction rates, promoting rapid resolutions. The use of chloroform as solvent allows the use of ambient air as the terminal oxidant at 23 degrees C, resulting in enhanced catalyst selectivity. These improved reaction conditions have permitted the successful kinetic resolution of benzylic, allylic, and cyclopropyl secondary alcohols to high enantiomeric excess with good-to-excellent selectivity factors. This catalyst system has also been applied to the desymmetrization of meso-diols, providing high yields of enantioenriched hydroxyketones.

  16. A 11-Steps Total Synthesis of Magellanine through a Gold(I)-Catalyzed Dehydro Diels-Alder Reaction. (United States)

    McGee, Philippe; Bétournay, Geneviève; Barabé, Francis; Barriault, Louis


    We have developed an innovative strategy for the formation of angular carbocycles via a gold(I)-catalyzed dehydro Diels-Alder reaction. This transformation provides rapid access to a variety of complex angular cores in excellent diastereoselectivities and high yields. The usefulness of this AuI -catalyzed cycloaddition was further demonstrated by accomplishing a 11-steps total synthesis of (±)-magellanine. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. On the Effect of Microwave Energy on Lipase-Catalyzed Polycondensation Reactions

    Directory of Open Access Journals (Sweden)

    Alessandro Pellis


    Full Text Available Microwave energy (MWe is, nowadays, widely used as a clean synthesis tool to improve several chemical reactions, such as drug molecule synthesis, carbohydrate conversion and biomass pyrolysis. On the other hand, its exploitation in enzymatic reactions has only been fleetingly investigated and, hence, further study of MWe is required to reach a precise understanding of its potential in this field. Starting from the authors’ experience in clean synthesis and biocatalyzed reactions, this study sheds light on the possibility of using MWe for enhancing enzyme-catalyzed polycondensation reactions and pre-polymer formation. Several systems and set ups were investigated involving bulk and organic media (solution phase reactions, different enzymatic preparations and various starting bio-based monomers. Results show that MWe enables the biocatalyzed synthesis of polyesters and pre-polymers in a similar way to that reported using conventional heating with an oil bath, but in a few cases, notably bulk phase polycondensations under intense microwave irradiation, MWe leads to a rapid enzyme deactivation.

  18. Vanadium pentoxide nanoparticles mimic vanadium haloperoxidases and thwart biofilm formation (United States)

    Natalio, Filipe; André, Rute; Hartog, Aloysius F.; Stoll, Brigitte; Jochum, Klaus Peter; Wever, Ron; Tremel, Wolfgang


    Marine biofouling--the colonization of small marine microorganisms on surfaces that are directly exposed to seawater, such as ships' hulls--is an expensive problem that is currently without an environmentally compatible solution. Biofouling leads to increased hydrodynamic drag, which, in turn, causes increased fuel consumption and greenhouse gas emissions. Tributyltin-free antifouling coatings and paints based on metal complexes or biocides have been shown to efficiently prevent marine biofouling. However, these materials can damage the environment through metal leaching (for example, of copper and zinc) and bacteria resistance. Here, we show that vanadium pentoxide nanowires act like naturally occurring vanadium haloperoxidases to prevent marine biofouling. In the presence of bromide ions and hydrogen peroxide, the nanowires catalyse the oxidation of bromide ions to hypobromous acid (HOBr). Singlet molecular oxygen (1O2) is formed and this exerts strong antibacterial activity, which prevents marine biofouling without being toxic to marine biota. Vanadium pentoxide nanowires have the potential to be an alternative approach to conventional anti-biofouling agents.

  19. Effect of osmolytes on protein dynamics in the lactate dehydrogenase-catalyzed reaction. (United States)

    Zhadin, Nickolay; Callender, Robert


    Laser-induced temperature jump relaxation spectroscopy was used to probe the effect of osmolytes on the microscopic rate constants of the lactate dehydrogenase-catalyzed reaction. NADH fluorescence and absorption relaxation kinetics were measured for the lactate dehydrogenase (LDH) reaction system in the presence of varying amounts of trimethylamine N-oxide (TMAO), a protein-stabilizing osmolyte, or urea, a protein-destabilizing osmolyte. Trimethylamine N-oxide (TMAO) at a concentration of 1 M strongly increases the rate of hydride transfer, nearly nullifies its activation energy, and also slightly increases the enthalpy of hydride transfer. In 1 M urea, the hydride transfer enthalpy is almost nullified, but the activation energy of the step is not affected significantly. TMAO increases the preference of the closed conformation of the active site loop in the LDH·NAD(+)·lactate complex; urea decreases it. The loop opening rate in the LDH·NADH·pyruvate complex changes its temperature dependence to inverse Arrhenius with TMAO. In this complex, urea accelerates the loop motion, without changing the loop opening enthalpy. A strong, non-Arrhenius decrease in the pyruvate binding rate in the presence of TMAO offers a decrease in the fraction of the open loop, pyruvate binding competent form at higher temperatures. The pyruvate off rate is not affected by urea but decreases with TMAO. Thus, the osmolytes strongly affect the rates and thermodynamics of specific events along the LDH-catalyzed reaction: binding of substrates, loop closure, and the chemical event. Qualitatively, these results can be understood as an osmolyte-induced change in the energy landscape of the protein complexes, shifting the conformational nature of functional substates within the protein ensemble.

  20. Biocatalytic carbon capture via reversible reaction cycle catalyzed by isocitrate dehydrogenase. (United States)

    Xia, Shunxiang; Frigo-Vaz, Benjamin; Zhao, Xueyan; Kim, Jungbae; Wang, Ping


    The practice of carbon capture and storage (CCS) requires efficient capture and separation of carbon dioxide from its gaseous mixtures such as flue gas, followed by releasing it as a pure gas which can be subsequently compressed and injected into underground storage sites. This has been mostly achieved via reversible thermochemical reactions which are generally energy-intensive. The current work examines a biocatalytic approach for carbon capture using an NADP(H)-dependent isocitrate dehydrogenase (ICDH) which catalyzes reversibly carboxylation and decarboxylation reactions. Different from chemical carbon capture processes that rely on thermal energy to realize purification of carbon dioxide, the biocatalytic strategy utilizes pH to leverage the reaction equilibrium, thereby realizing energy-efficient carbon capture under ambient conditions. Results showed that over 25 mol of carbon dioxide could be captured and purified from its gas mixture for each gram of ICDH applied for each carboxylation/decarboxylation reaction cycle by varying pH between 6 and 9. This work demonstrates the promising potentials of pH-sensitive biocatalysis as a green-chemistry route for carbon capture. Copyright © 2014. Published by Elsevier Inc.

  1. Baker's yeast catalyzed asymmetric reduction of prochiral ketones in different reaction mediums

    Directory of Open Access Journals (Sweden)

    Adi Wolfson


    Full Text Available Baker’s yeast catalyzes the asymmetric reduction of prochiral ketones in water and in various organic solvents. The reaction in water, which is the first solvent of choice for bio-reactions, led to a high product yield and enantiomeric excess, but the low miscibility of organic molecules in water resulted in lower conversions when more hydrophobic ketones were used. Petroleum-based solvents such as hexane and petroleum ether were also successfully employed as reaction mediums, but the viability of the yeast in these solvents was negligible, and they have severe environmental impacts due to their high toxicity levels. Performing the reaction in green solvents, like ionic liquids, fluorous media, and glycerol-based solvents, which have low volatilities and can be recycled, enabled dissolution of the substrates and of the energy source and also promoted isolation of the product. Among all tested green solvents, glycerol-based solvents are preferable due to their biodegradable natures and their origins from renewable sources.

  2. Beta-D-xylosidase from Selenomonas ruminantium: catalyzed reactions with natural and artificial substrates. (United States)

    Jordan, Douglas B


    Catalytically efficient beta-D-xylosidase from Selenomonas ruminantium (SXA) exhibits pK (a)s 5 and 7 (assigned to catalytic base, D14, and catalytic acid, E186) for k (cat)/K (m) with substrates 1,4-beta-D-xylobiose (X2) and 1,4-beta-D-xylotriose (X3). Catalytically inactive, dianionic SXA (D14(-)E186(-)) has threefold lower affinity than catalytically active, monoanionic SXA (D14(-)E186(H)) for X2 and X3, whereas D14(-)E186(-) has twofold higher affinity than D14(-)E186(H) for 4-nitrophenyl-beta-D-xylopyranoside (4NPX), and D14(-)E186(-) has no affinity for 4-nitrophenyl-alpha-L-arabinofuranoside. Anomeric isomers, alpha-D-xylose and beta-D-xylose, have similar affinity for SXA. 4-Nitrophenol competitively inhibits SXA-catalyzed hydrolysis of 4NPX. SXA steady-state kinetic parameters account for complete progress curves of SXA-catalyzed hydrolysis reactions.

  3. Prediction of oxidoreductase-catalyzed reactions based on atomic properties of metabolites. (United States)

    Mu, Fangping; Unkefer, Pat J; Unkefer, Clifford J; Hlavacek, William S


    Our knowledge of metabolism is far from complete, and the gaps in our knowledge are being revealed by metabolomic detection of small-molecules not previously known to exist in cells. An important challenge is to determine the reactions in which these compounds participate, which can lead to the identification of gene products responsible for novel metabolic pathways. To address this challenge, we investigate how machine learning can be used to predict potential substrates and products of oxidoreductase-catalyzed reactions. We examined 1956 oxidation/reduction reactions in the KEGG database. The vast majority of these reactions (1626) can be divided into 12 subclasses, each of which is marked by a particular type of functional group transformation. For a given transformation, the local structures of reaction centers in substrates and products can be characterized by patterns. These patterns are not unique to reactants but are widely distributed among KEGG metabolites. To distinguish reactants from non-reactants, we trained classifiers (linear-kernel Support Vector Machines) using negative and positive examples. The input to a classifier is a set of atomic features that can be determined from the 2D chemical structure of a compound. Depending on the subclass of reaction, the accuracy of prediction for positives (negatives) is 64 to 93% (44 to 92%) when asking if a compound is a substrate and 71 to 98% (50 to 92%) when asking if a compound is a product. Sensitivity analysis reveals that this performance is robust to variations of the training data. Our results suggest that metabolic connectivity can be predicted with reasonable accuracy from the presence or absence of local structural motifs in compounds and their readily calculated atomic features. Classifiers reported here can be used freely for noncommercial purposes via a Java program available upon request.

  4. Evidencing an inner-sphere mechanism for NHC-Au(I-catalyzed carbene-transfer reactions from ethyl diazoacetate

    Directory of Open Access Journals (Sweden)

    Manuel R. Fructos


    Full Text Available Kinetic experiments based on the measurement of nitrogen evolution in the reaction of ethyl diazoacetate (N2CHCO2Et, EDA and styrene or methanol catalyzed by the [IPrAu]+ core (IPr = 1,3-bis(diisopropylphenylimidazole-2-ylidene have provided evidence that the transfer of the carbene group CHCO2Et to the substrate (styrene or methanol takes place in the coordination sphere of Au(I by means of an inner-sphere mechanism, in contrast to the generally accepted proposal of outer-sphere mechanisms for Au(I-catalyzed reactions.

  5. Isotope Effects as Probes for Enzyme Catalyzed Hydrogen-Transfer Reactions

    Directory of Open Access Journals (Sweden)

    Amnon Kohen


    Full Text Available Kinetic Isotope effects (KIEs have long served as a probe for the mechanisms of both enzymatic and solution reactions. Here, we discuss various models for the physical sources of KIEs, how experimentalists can use those models to interpret their data, and how the focus of traditional models has grown to a model that includes motion of the enzyme and quantum mechanical nuclear tunneling. We then present two case studies of enzymes, thymidylate synthase and alcohol dehydrogenase, and discuss how KIEs have shed light on the C-H bond cleavages those enzymes catalyze. We will show how the combination of both experimental and computational studies has changed our notion of how these enzymes exert their catalytic powers.

  6. Analyzing site selectivity in Rh2(esp)2-catalyzed intermolecular C-H amination reactions. (United States)

    Bess, Elizabeth N; DeLuca, Ryan J; Tindall, Daniel J; Oderinde, Martins S; Roizen, Jennifer L; Du Bois, J; Sigman, Matthew S


    Predicting site selectivity in C-H bond oxidation reactions involving heteroatom transfer is challenged by the small energetic differences between disparate bond types and the subtle interplay of steric and electronic effects that influence reactivity. Herein, the factors governing selective Rh2(esp)2-catalyzed C-H amination of isoamylbenzene derivatives are investigated, where modification to both the nitrogen source, a sulfamate ester, and substrate are shown to impact isomeric product ratios. Linear regression mathematical modeling is used to define a relationship that equates both IR stretching parameters and Hammett σ(+) values to the differential free energy of benzylic versus tertiary C-H amination. This model has informed the development of a novel sulfamate ester, which affords the highest benzylic-to-tertiary site selectivity (9.5:1) observed for this system.

  7. Heterometallic Metal-Organic Frameworks That Catalyze Two Different Reactions Sequentially. (United States)

    Saha, Debraj; Hazra, Dipak K; Maity, Tanmoy; Koner, Subratanath


    A series of copper- and alkaline-earth-metal-based multidimensional metal-organic frameworks, {[CuMg(pdc)2(H2O)4]·2H2O}n (1), [CuCa(pdc)2]n (2), [CuSr(pdc)2(H2O)3]n (3), and {[CuBa(pdc)2(H2O)5]·H2O}n (4), where H2Pdc = pyridine-2,5-dicarboxylic acid, were hydrothermally synthesized and characterized. Two different metals act as the active center to catalyze two kinds of reactions, viz., olefin to its epoxide followed by epoxide ring opening to afford the corresponding vicinal diol in a sequential manner.

  8. Transition-metal-catalyzed carbonylation reactions of olefins and alkynes: a personal account. (United States)

    Wu, Xiao-Feng; Fang, Xianjie; Wu, Lipeng; Jackstell, Ralf; Neumann, Helfried; Beller, Matthias


    Carbon monoxide was discovered and identified in the 18th century. Since the first applications in industry 80 years ago, academic and industrial laboratories have broadly explored CO's use in chemical reactions. Today organic chemists routinely employ CO in organic chemistry to synthesize all kinds of carbonyl compounds. Despite all these achievements and a century of carbonylation catalysis, many important research questions and challenges remain. Notably, apart from academic developments, industry applies carbonylation reactions with CO on bulk scale. In fact, today the largest applications of homogeneous catalysis (regarding scale) are carbonylation reactions, especially hydroformylations. In addition, the vast majority of acetic acid is produced via carbonylation of methanol (Monsanto or Cativa process). The carbonylation of olefins/alkynes with nucleophiles, such as alcohols and amines, represent another important type of such reactions. In this Account, we discuss our work on various carbonylations of unsaturated compounds and related reactions. Rhodium-catalyzed isomerization and hydroformylation reactions of internal olefins provide straightforward access to higher value aldehydes. Catalytic hydroaminomethylations offer an ideal way to synthesize substituted amines and even heterocycles directly. More recently, our group has also developed so-called alternative metal catalysts based on iridium, ruthenium, and iron. What about the future of carbonylation reactions? CO is already one of the most versatile C1 building blocks for organic synthesis and is widely used in industry. However, because of CO's high toxicity and gaseous nature, organic chemists are often reluctant to apply carbonylations more frequently. In addition, new regulations have recently made the transportation of carbon monoxide more difficult. Hence, researchers will need to develop and more frequently use practical and benign CO-generating reagents. Apart from formates, alcohols, and metal

  9. Kinetic study of free fatty acid esterification reaction catalyzed by recoverable and reusable hydrochloric acid. (United States)

    Su, Chia-Hung


    The catalytic performance and recoverability of several homogeneous acid catalysts (hydrochloric, sulfuric, and nitric acids) for the esterification of enzyme-hydrolyzed free fatty acid (FFA) and methanol were studied. Although all tested catalysts drove the reaction to a high yield, hydrochloric acid was the only catalyst that could be considerably recovered and reused. The kinetics of the esterification reaction catalyzed by hydrochloric acid was investigated under varying catalyst loading (0.1-1M), reaction temperature (303-343K), and methanol/FFA molar ratio (1:1-20:1). In addition, a pseudo-homogeneous kinetic model incorporating the above factors was developed. A good agreement (r(2)=0.98) between the experimental and calculated data was obtained, thus proving the reliability of the model. Furthermore, the reusability of hydrochloric acid in FFA esterification can be predicted by the developed model. The recoverable hydrochloric acid achieved high yields of FFA esterification within five times of reuse. Copyright © 2012 Elsevier Ltd. All rights reserved.

  10. New Stetter reactions catalyzed by thiamine diphosphate dependent MenD from E. coli. (United States)

    Beigi, Maryam; Waltzer, Simon; Zarei, Mostafa; Müller, Michael


    The intermolecular asymmetric Stetter reaction is a rarely found biocatalysts transformation. MenD, the second enzyme of the menaquinone biosynthetic pathway, catalyzes as a physiological reaction a Stetter-like addition of α-ketoglutarate to isochorismate. The substrate range of MenD for similar 1,4-additions is highly restricted. All other thiamine diphosphate dependent enzymes known to act as stetterases are members of the PigD enzyme subfamily, which accept aliphatic and aromatic α,β-unsaturated ketones and thioesters as Michael acceptor substrates. Here, we describe the unexpected activity of MenD with short-chain α,β-unsaturated acids and derivatives as substrates in Stetter reactions. MenD possesses a characteristic substrate range with respect to Michael acceptor substrates which is distinctly different from the classical stetterases. This provides biocatalytic access to new types of products which are not related to the products currently accessible by thiamine diphosphate dependent enzyme catalysis. Copyright © 2014 Elsevier B.V. All rights reserved.

  11. Transition metal-catalyzed C-H bond functionalization in multicomponent reactions: a tool toward molecular diversity. (United States)

    Wan, Jie-Ping; Gan, Lu; Liu, Yunyun


    Transition metal-catalyzed C-H bond functionalization has numerous applications in organic synthesis as a powerful type of bond transformation. In particular, the combination of C-H functionalization with other types of chemical transformations in the manner of multicomponent reactions is an even more beneficial tool in the synthesis of small organic molecules because such reactions provide a platform for the rapid generation of high molecular diversity and complexity by making use of the advantages of both latent C-H bond transformation and the multicomponent reaction. Herein, we provide a review highlighting the research advances in the multicomponent reactions built upon transition metal-catalyzed C-H bond functionalization. The content spans from the reactions featuring the functionalization of C(sp(3))-H, C(sp(2))-H and C(sp)-H bonds over the last decade.

  12. Haloperoxidase-like activity in spruce forest soil. A source of volatile halogenated organic compounds?

    DEFF Research Database (Denmark)

    Laturnus, F.; Mehrtens, G.; Grøn, C.


    Haloperoxidase-like activity was monitored in samples from a podzol soil in an uncontaminated spruce forest at Klosterhede, Denmark. Activity for the oxidation of chloride and bromide was found. The pH optima for chlorination and bromination ranged between pH 2.5 and 4: Very high activity, up to ...

  13. Nafion®-catalyzed microwave-assisted Ritter reaction: An atom-economic solvent-free synthesis of amides (United States)

    An atom-economic solvent-free synthesis of amides by the Ritter reaction of alcohols and nitriles under microwave irradiation is reported. This green protocol is catalyzed by solid supported Nafion®NR50 with improved efficiency and reduced waste production.

  14. An Efficient Synthesis of Substituted Quinolines via Indium(III) Chloride Catalyzed Reaction of Imines with Alkynes

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, Mei; Fu, Weijun; Xun, Chen [Luoyang Normal University, Luoyang (China); Zou, Guanglong [Guizhou University for Nationalities, Guiyang (China)


    An efficient synthetic method for the preparation of quinolines through indium(III) chloride-catalyzed tandem addition-cyclization-oxidation reactions of imines with alkynes was developed. The processes can provide a diverse range of quinoline derivatives in good yields from simple imines and alkynes.

  15. Kinetic studies on the Rhizomucor miehei lipase catalyzed esterification reaction of oleic acid with 1-butanol in a biphasic system

    NARCIS (Netherlands)

    Kraai, G.N.; Winkelman, J.G.M.; de Vries, Johannes; Heeres, H.J.


    The kinetics of the esterification of oleic acid with 1 -butanol catalyzed by free Rhizomucor miehei lipase in a biphasic system was studied in a batch reactor. The reaction appeared to proceed via a Ping Pong bi-bi mechanism with I -butanol inhibition. The kinetic constants of the model were

  16. Iron-catalyzed direct synthesis of imines from amines or alcohols and amines via aerobic oxidative reactions under air. (United States)

    Zhang, Erlei; Tian, Haiwen; Xu, Sendong; Yu, Xiaochun; Xu, Qing


    Abundant and cheap iron readily catalyzed the aerobic oxidative reactions of primary amines, secondary amines, benzylamines with anilines, and alcohols with amines by directly using air as the economic and safe oxidant, providing several direct, practical, and greener approaches for the preparation of useful imines.

  17. Palladium-Catalyzed Cross-Coupling of Silyl Electrophiles with Alkylzinc Halides: A Silyl-Negishi Reaction. (United States)

    Cinderella, Andrew P; Vulovic, Bojan; Watson, Donald A


    We report the first example of a silyl-Negishi reaction between secondary zinc organometallics and silicon electrophiles. This palladium-catalyzed process provides direct access to alkyl silanes. The delicate balance of steric and electronic parameters of the employed DrewPhos ligand is paramount to suppressing isomerization and promoting efficient and selective cross-coupling.

  18. Insights into the formation of carlactone from in-depth analysis of the CCD8-catalyzed reactions

    KAUST Repository

    Bruno, Mark


    Strigolactones (SLs) are a new class of phytohormones synthesized from carotenoids via carlactone. The complex structure of carlactone is not easily deducible from its precursor, a cis-configured β-carotene cleavage product, and is thus formed via a poorly understood series of reactions and molecular rearrangements, all catalyzed by only one enzyme, the carotenoid cleavage dioxygenase 8 (CCD8). Moreover, the reactions leading to carlactone are expected to form a second, yet unidentified product. In this study, we used (13) C and (18) O-labelling to shed light on the reactions catalyzed by CCD8. The characterization of the resulting carlactone by LC-MS and NMR, and the identification of the assumed, less accessible second product allowed us to formulate a minimal reaction mechanism for carlactone generation. This article is protected by copyright. All rights reserved.

  19. Palladium(II-catalyzed Heck reaction of aryl halides and arylboronic acids with olefins under mild conditions

    Directory of Open Access Journals (Sweden)

    Tanveer Mahamadali Shaikh


    Full Text Available A series of general and selective Pd(II-catalyzed Heck reactions were investigated under mild reaction conditions. The first protocol has been developed employing an imidazole-based secondary phosphine oxide (SPO ligated palladium complex (6 as a precatalyst. The catalytic coupling of aryl halides and olefins led to the formation of the corresponding coupled products in excellent yields. A variety of substrates, both electron-rich and electron-poor olefins, were converted smoothly to the targeted products in high yields. Compared with the existing approaches employing SPO–Pd complexes in a Heck reaction, the current strategy features mild reaction conditions and broad substrate scope. Furthermore, we described the coupling of arylboronic acids with olefins, which were catalyzed by Pd(OAc2 and employed N-bromosuccinimide as an additive under ambient conditions. The resulted biaryls have been obtained in moderate to good yields.

  20. Role of Long-Range Protein Dynamics in Different Thymidylate Synthase Catalyzed Reactions

    Directory of Open Access Journals (Sweden)

    Thelma Abeysinghe


    Full Text Available Recent studies of Escherichia coli thymidylate synthase (ecTSase showed that a highly conserved residue, Y209, that is located 8 Å away from the reaction site, plays a key role in the protein’s dynamics. Those crystallographic studies indicated that Y209W mutant is a structurally identical but dynamically altered relative to the wild type (WT enzyme, and that its turnover catalytic rate governed by a slow hydride-transfer has been affected. The most challenging test of an examination of a fast chemical conversion that precedes the rate-limiting step has been achieved here. The physical nature of both fast and slow C-H bond activations have been compared between the WT and mutant by means of observed and intrinsic kinetic isotope effects (KIEs and their temperature dependence. The findings indicate that the proton abstraction step has not been altered as much as the hydride transfer step. Additionally, the comparison indicated that other kinetic steps in the TSase catalyzed reaction were substantially affected, including the order of the substrate binding. Enigmatically, although Y209 is H-bonded to 3'-OH of 2'-deoxyuridine-5'-mono­phosphate (dUMP, its altered dynamics is more pronounced on the binding of the remote cofactor, (6R-N5,N10-methylene-5,6,7,8-tetrahydrofolate (CH2H4folate, revealing the importance of long-range dynamics of the enzymatic complex and its catalytic function.

  1. Methyl Ester Production via Heterogeneous Acid-Catalyzed Simultaneous Transesterification and Esterification Reactions (United States)

    Indrayanah, S.; Erwin; Marsih, I. N.; Suprapto; Murwani, I. K.


    The heterogeneous acid catalysts (MgF2 and ZnF2) have been used to catalyze the simultaneous transesterification and esterification reactions of crude palm oil (CPO) with methanol. Catalysts were synthesized by sol-gel method (combination of fluorolysis and hydrolysis). The physicochemical, structural, textural, thermal stability of the prepared catalysts was investigated by N2 adsorption-desorption, XRD, FT-IR, SEM and TG/DTG. Both MgF2 and ZnF2 have rutile structures with a different phase. The surface area of ZnF2 is smaller than that of MgF2, but the pore size and volume of ZnF2 are larger than those of MgF2. However, these materials are thermally stable. The performance of the catalysts is determined from the yield of catalysts toward the formation of methyl ester determined based on the product of methyl ester obtained from the reaction. The catalytic activity of ZnF2 is higher than MgF2 amounted to 85.21% and 26.82% with the optimum condition. The high activity of ZnF2 could be attributed to its pore diameter and pore volume but was not correlated with its surface area. The yield of methyl ester decreased along with the increase in molar ratio of methanol/CPO from 85.21 to 80.99 for ZnF2, respectively.

  2. Possible pathophysiological roles of transglutaminase-catalyzed reactions in the pathogenesis of human neurodegenerative diseases

    Directory of Open Access Journals (Sweden)

    Enrica Serretiello


    Full Text Available Transglutaminases (TG, E.C. are related and ubiquitous enzymes that catalyze the cross linking of a glutaminyl residue of a protein/peptide substrate to a lysyl residue of a protein/peptide co-substrate. These enzymes are also capable of catalyzing other post-translational reactions important for cell life. The distribution and the physiological roles of human TGs have been widely studied in numerous cell types and tissues and recently their roles in several diseases have begun to be identified. It has been hypothesized that transglutaminase activity is directly involved in the pathogenetic mechanisms responsible for several human diseases. In particular, tissue TG (tTG, TG2, a member of the TG enzyme family, has been recently shown to be involved in the molecular mechanisms responsible for a very widespread human pathology, Celiac Disease (CD, one of the most common food intolerances described in the western population. The main food agent that provokes the strong and diffuse clinical symptoms has been known for several years to be gliadin, a protein present in a very large number of human foods derived from vegetables. Recently, some biochemical and immunological aspects of this very common disease have been clarified, and “tissue” transglutaminase, a multifunctional and ubiquitous enzyme, has been identified as one of the major factors. The aim of this review is to summarize the most recent findings concerning the relationships between the biochemical properties of the transglutaminase activity and the basic molecular mechanisms responsible for some human diseases, with particular reference to neuropsychiatric disorders. Possible molecular links between CD and neuropsychiatric disorders, and the use of transglutaminase inhibitors are also discussed.

  3. The bacterial catabolism of polycyclic aromatic hydrocarbons: Characterization of three hydratase-aldolase-catalyzed reactions

    Directory of Open Access Journals (Sweden)

    Jake A. LeVieux


    Full Text Available Polycyclic aromatic hydrocarbons (PAHs are highly toxic, pervasive environmental pollutants with mutagenic, teratogenic, and carcinogenic properties. There is interest in exploiting the nutritional capabilities of microbes to remove PAHs from various environments including those impacted by improper disposal or spills. Although there is a considerable body of literature on PAH degradation, the substrates and products for many of the enzymes have never been identified and many proposed activities have never been confirmed. This is particularly true for high molecular weight PAHs (e.g., phenanthrene, fluoranthene, and pyrene. As a result, pathways for the degradation of these compounds are proposed to follow one elucidated for naphthalene with limited experimental verification. In this pathway, ring fission produces a species that can undergo a non-enzymatic cyclization reaction. An isomerase opens the ring and catalyzes a cis to trans double bond isomerization. The resulting product is the substrate for a hydratase-aldolase, which catalyzes the addition of water to the double bond of an α,β-unsaturated ketone, followed by a retro-aldol cleavage. Initial kinetic and mechanistic studies of the hydratase-aldolase in the naphthalene pathway (designated NahE and two hydratase-aldolases in the phenanthrene pathway (PhdG and PhdJ have been completed. Crystallographic work on two of the enzymes (NahE and PhdJ provides a rudimentary picture of the mechanism and a platform for future work to identify the structural basis for catalysis and the individual specificities of these hydratase-aldolases.

  4. Enantioselective Direct Mannich-Type Reactions Catalyzed by Frustrated Lewis Acid/Brønsted Base Complexes. (United States)

    Shang, Ming; Cao, Min; Wang, Qifan; Wasa, Masayuki


    An enantioselective direct Mannich-type reaction catalyzed by a sterically frustrated Lewis acid/Brønsted base complex is disclosed. Cooperative functioning of the chiral Lewis acid and achiral Brønsted base components gives rise to in situ enolate generation from monocarbonyl compounds. Subsequent reaction with hydrogen-bond-activated aldimines delivers β-aminocarbonyl compounds with high enantiomeric purity. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Lipase-Catalyzed Synthesis of Indolyl 4H-Chromenes via a Multicomponent Reaction in Ionic Liquid

    Directory of Open Access Journals (Sweden)

    Weian Zhang


    Full Text Available Synthesis of indolyl 4H-chromenes via a three-component reaction catalyzed by lipase in ionic liquidsis reported here for the first time. High yields (77–98% were obtained when Mucor miehei lipase was used as the catalyst in [EMIM][BF4]. Furthermore, [EMIM][BF4] exhibited good reusability in this enzymatic reaction. This study affords a new example of lipase catalytic promiscuity and broadens the application range of ionic liquid in biocatalysis.

  6. The interaction of luciferase, flavin mono-nucleotide and long-chain aldehydes in the light reaction catalyzed by preparations of luminous bacteria

    NARCIS (Netherlands)

    Terpstra, Willeke


    The light reaction catalyzed by a luciferase preparation of a dark strain of Photobacterium splendidum, probably containing a slightly altered luciferase molecule, was compared with the light reaction catalyzed by a similar preparation of a brightly luminescent strain of Photobacterium phosphoreum.

  7. Ab initio calculations concerning the reaction mechanism of the copper(II) catalyzed glycine condensation in aqueous sodium chloride solution (United States)

    Liedl, Klaus R.; Rode, Bernd M.


    Starting from results of detailed experimental work concerning the copper(II) catalyzed glycine condensation, quantum-mechanical studies of species which should be relevant for the reaction mechanism are presented. This reaction is of special interest because it could be important in explaining the formation of the first peptides on prebiotic earth. SCF geometry optimizations of aquo-chloro-glycinato—copper(II) complexes at Hartree—Fock level were performed especially to study the necessity of chlorine for the reaction. In that way a hypothetical reaction mechanism could be confirmed. Structural distortions as expected from the Jahn—Teller effect resulted from optimizations of copper complexes in C1 geometry.

  8. DNA and Protein Requirements for Substrate Conformational Changes Necessary for Human Flap Endonuclease-1-catalyzed Reaction* (United States)

    Algasaier, Sana I.; Exell, Jack C.; Bennet, Ian A.; Thompson, Mark J.; Gotham, Victoria J. B.; Shaw, Steven J.; Craggs, Timothy D.; Finger, L. David; Grasby, Jane A.


    Human flap endonuclease-1 (hFEN1) catalyzes the essential removal of single-stranded flaps arising at DNA junctions during replication and repair processes. hFEN1 biological function must be precisely controlled, and consequently, the protein relies on a combination of protein and substrate conformational changes as a prerequisite for reaction. These include substrate bending at the duplex-duplex junction and transfer of unpaired reacting duplex end into the active site. When present, 5′-flaps are thought to thread under the helical cap, limiting reaction to flaps with free 5′-termini in vivo. Here we monitored DNA bending by FRET and DNA unpairing using 2-aminopurine exciton pair CD to determine the DNA and protein requirements for these substrate conformational changes. Binding of DNA to hFEN1 in a bent conformation occurred independently of 5′-flap accommodation and did not require active site metal ions or the presence of conserved active site residues. More stringent requirements exist for transfer of the substrate to the active site. Placement of the scissile phosphate diester in the active site required the presence of divalent metal ions, a free 5′-flap (if present), a Watson-Crick base pair at the terminus of the reacting duplex, and the intact secondary structure of the enzyme helical cap. Optimal positioning of the scissile phosphate additionally required active site conserved residues Tyr40, Asp181, and Arg100 and a reacting duplex 5′-phosphate. These studies suggest a FEN1 reaction mechanism where junctions are bound and 5′-flaps are threaded (when present), and finally the substrate is transferred onto active site metals initiating cleavage. PMID:26884332

  9. Dynamic and Electrostatic Effects on the Reaction Catalyzed by HIV-1 Protease. (United States)

    Krzemińska, Agnieszka; Moliner, Vicent; Świderek, Katarzyna


    HIV-1 Protease (HIV-1 PR) is one of the three enzymes essential for the replication process of HIV-1 virus, which explains why it has been the main target for design of drugs against acquired immunodeficiency syndrome (AIDS). This work is focused on exploring the proteolysis reaction catalyzed by HIV-1 PR, with special attention to the dynamic and electrostatic effects governing its catalytic power. Free energy surfaces for all possible mechanisms have been computed in terms of potentials of mean force (PMFs) within hybrid QM/MM potentials, with the QM subset of atoms described at semiempirical (AM1) and DFT (M06-2X) level. The results suggest that the most favorable reaction mechanism involves formation of a gem-diol intermediate, whose decomposition into the product complex would correspond to the rate-limiting step. The agreement between the activation free energy of this step with experimental data, as well as kinetic isotope effects (KIEs), supports this prediction. The role of the protein dynamic was studied by protein isotope labeling in the framework of the Variational Transition State Theory. The predicted enzyme KIEs, also very close to the values measured experimentally, reveal a measurable but small dynamic effect. Our calculations show how the contribution of dynamic effects to the effective activation free energy appears to be below 1 kcal·mol(-1). On the contrary, the electric field created by the protein in the active site of the enzyme emerges as being critical for the electronic reorganization required during the reaction. These electrostatic properties of the active site could be used as a mold for future drug design.

  10. Asymmetric Cycloaddition and Cyclization Reactions Catalyzed by Chiral N,N'-Dioxide-Metal Complexes. (United States)

    Liu, Xiaohua; Zheng, Haifeng; Xia, Yong; Lin, Lili; Feng, Xiaoming


    Catalytic asymmetric cycloadditions and cascade cyclizations are a major focus for the enantioselective construction of chiral carbo- and heterocycles. A number of chiral Lewis acids and organocatalysts have been designed for such reactions. The development of broadly applicable catalysts bearing novel chiral backbones to meet the demands of various applications is an ongoing challenge. Approximately 10 years ago, we introduced a group of conformationally flexible C2-symmetric N,N'-dioxide amide compounds, which represent a new class of privileged ligands. The coordination of the four oxygens of a chiral N,N'-dioxide around a central metal generates an octahedral tricyclometalated Lewis acid catalyst that can carry out various enantioselective reactions. In this Account, we summarize our recent studies on asymmetric cycloadditions between various dienophiles and dienes, dipoles and dipolarophiles, and cascade cyclizations catalyzed by chiral N,N'-dioxide-metal complexes. In principle, these unique chiral catalysts lower the LUMO energy of electron-deficient 2π components or heterodienes by coordination with the functional groups via various binding modes. With N-Boc-3-alkenyloxindole and alkylidene malonate as the electron-deficient 2π components, N,N'-dioxide-metal complexes provided excellent catalytic activities and asymmetric inductions for a variety of transformations, including [2 + 1], [3 + 2], [4 + 2], and [8 + 2] cycloadditions. Mechanistically, these substrates could be efficiently activated through bidentate coordination. The strategy was also useful for asymmetric cascade cyclizations to form polycyclic adducts. Monodentate or bidentate coordination of other α,β-unsubstituted carbonyl compounds to metal centers enabled both normal Diels-Alder reactions and inverse-electron-demand hetero-Diels-Alder reactions as well as [2 + 2] additions. Furthermore, hetero-Diels-Alder reactions of aldehydes, ketones, and imines are well-tolerated and afford various

  11. Rhodium-catalyzed cross-coupling reaction of arylboronates and diazoesters and tandem alkylation reaction for the synthesis of quaternary α,α-heterodiaryl carboxylic esters. (United States)

    Tsoi, Yuk-Tai; Zhou, Zhongyuan; Yu, Wing-Yiu


    A rhodium-catalyzed one-pot three-component coupling reaction was developed for the synthesis of quaternary α,α-heterodiaryl carboxylic esters. This reaction involves cross-coupling of the arylrhodium(I) complexes with α-aryldiazoacetates to form oxa-π-allylrhodium complexes. With KOtBu and alkyl halides, tandem alkylation of the allyl complex occurs to form a quaternary stereocenter at the carbenic carbon. © 2011 American Chemical Society

  12. Effect of mass transfer on the oxygen reduction reaction catalyzed by platinum dendrimer encapsulated nanoparticles (United States)

    Dumitrescu, Ioana; Crooks, Richard M.


    Here we report on the effect of the mass transfer rate (kt) on the oxygen reduction reaction (ORR) catalyzed by Pt dendrimer-encapsulated nanoparticles (DENs) comprised of 147 and 55 atoms (Pt147 and Pt55). The experiments were carried out using a dual-electrode microelectrochemical device, which enables the study of the ORR under high kt conditions with simultaneous detection of H2O2. At low kt (0.02 to 0.12 cm s-1) the effective number of electrons involved in ORR, neff, is 3.7 for Pt147 and 3.4 for Pt55. As kt is increased, the mass-transfer-limited current for the ORR becomes significantly lower than the value predicted by the Levich equation for a 4-electron process regardless of catalyst size. However, the percentage of H2O2 detected remains constant, such that neff barely changes over the entire kt range explored (0.02 cm s-1). This suggests that mass transfer does not affect neff, which has implications for the mechanism of the ORR on Pt nanoparticles. Interestingly, there is a significant difference in neff for the two sizes of Pt DENs (neff = 3.7 and 3.5 for Pt147 and Pt55, respectively) that cannot be assigned to mass transfer effects and that we therefore attribute to a particle size effect. PMID:22665772

  13. Mechanisms and Origins of Selectivities of the Lewis Acid-Catalyzed Diels-Alder Reactions between Arylallenes and Acrylates. (United States)

    Yu, Peiyuan; Li, Wei; Houk, K N


    The mechanisms of recently reported Lewis acid-catalyzed Diels-Alder reactions of arylallenes and acrylates were studied using density functional theory calculations. A stepwise mechanism involving short-lived zwitterion intermediates is established. The reaction is endo-selective in the presence of Lewis acid catalyst. The [2 + 2] cycloaddition is not observed because of the greater charge separation in the first step of the [2 + 2] cycloaddition. The origins of chirality transfer in the Diels-Alder reaction using chiral arylallenes are uncovered, and the absolute stereochemistry of the product is predicted.

  14. N-Heterocyclic Carbene-Catalyzed Vinylogous Mukaiyama Aldol Reaction of α-Keto Esters and α-Trifluoromethyl Ketones

    KAUST Repository

    Du, Guang-Fen


    © Georg Thieme Verlag Stuttgart · New York · Synthesis 2016. N-Heterocyclic carbene (NHC)-catalyzed vinylogous Mukaiyama aldol reaction of ketones was developed. Under the catalysis of 5 mol% NHC, α-keto esters and α-trifluoromethyl ketones reacted with 2-(trimethysilyloxy)furan efficiently to produce γ-substituted butenolides containing adjacent quaternary and tertiary carbon centers in high yields with good diastereoselectivities.

  15. In Vivo and in Vitro Evidence for Biochemical Coupling of Reactions Catalyzed by Lysophosphatidylcholine Acyltransferase and Diacylglycerol Acyltransferase* (United States)

    Pan, Xue; Chen, Guanqun; Kazachkov, Michael; Greer, Michael S.; Caldo, Kristian Mark P.; Zou, Jitao; Weselake, Randall J.


    Seed oils of flax (Linum usitatissimum L.) and many other plant species contain substantial amounts of polyunsaturated fatty acids (PUFAs). Phosphatidylcholine (PC) is the major site for PUFA synthesis. The exact mechanisms of how these PUFAs are channeled from PC into triacylglycerol (TAG) needs to be further explored. By using in vivo and in vitro approaches, we demonstrated that the PC deacylation reaction catalyzed by the reverse action of acyl-CoA:lysophosphatidylcholine acyltransferase (LPCAT) can transfer PUFAs on PC directly into the acyl-CoA pool, making these PUFAs available for the diacylglycerol acyltransferase (DGAT)-catalyzed reaction for TAG production. Two types of yeast mutants were generated for in vivo and in vitro experiments, respectively. Both mutants provide a null background with no endogenous TAG forming capacity and an extremely low LPCAT activity. In vivo experiments showed that co-expressing flax DGAT1-1 and LPCAT1 in the yeast quintuple mutant significantly increased 18-carbon PUFAs in TAG with a concomitant decrease of 18-carbon PUFAs in phospholipid. We further showed that after incubation of sn-2-[14C]acyl-PC, formation of [14C]TAG was only possible with yeast microsomes containing both LPCAT1 and DGAT1-1. Moreover, the specific activity of overall LPCAT1 and DGAT1-1 coupling process exhibited a preference for transferring 14C-labeled linoleoyl or linolenoyl than oleoyl moieties from the sn-2 position of PC to TAG. Together, our data support the hypothesis of biochemical coupling of the LPCAT1-catalyzed reverse reaction with the DGAT1-1-catalyzed reaction for incorporating PUFAs into TAG. This process represents a potential route for enriching TAG in PUFA content during seed development in flax. PMID:26055703

  16. Benzylation Reactions in DMF Lead to an Impurity Which Acts as an Organocatalyst Poison in Thiourea-Catalyzed Glycosylations. (United States)

    Colgan, Avene C; Müller-Bunz, Helge; McGarrigle, Eoghan M


    The benzylation of alcohols with the commonly used combination of benzyl bromide and sodium hydride in DMF can lead to the formation of an amine side product, N,N'-dimethyl-1-phenyl-1-(o-tolyl)methanamine. This amine coeluted with benzylated galactal during column chromatography and was found to be a catalyst poison in thiourea-catalyzed glycosylations of galactals. It may also be problematic for other base-sensitive reactions involving benzylated substrates. Solutions to this problem are described.

  17. Energy-Related Small Molecule Activation Reactions: Oxygen Reduction and Hydrogen and Oxygen Evolution Reactions Catalyzed by Porphyrin- and Corrole-Based Systems. (United States)

    Zhang, Wei; Lai, Wenzhen; Cao, Rui


    Globally increasing energy demands and environmental concerns related to the use of fossil fuels have stimulated extensive research to identify new energy systems and economies that are sustainable, clean, low cost, and environmentally benign. Hydrogen generation from solar-driven water splitting is a promising strategy to store solar energy in chemical bonds. The subsequent combustion of hydrogen in fuel cells produces electric energy, and the only exhaust is water. These two reactions compose an ideal process to provide clean and sustainable energy. In such a process, a hydrogen evolution reaction (HER), an oxygen evolution reaction (OER) during water splitting, and an oxygen reduction reaction (ORR) as a fuel cell cathodic reaction are key steps that affect the efficiency of the overall energy conversion. Catalysts play key roles in this process by improving the kinetics of these reactions. Porphyrin-based and corrole-based systems are versatile and can efficiently catalyze the ORR, OER, and HER. Because of the significance of energy-related small molecule activation, this review covers recent progress in hydrogen evolution, oxygen evolution, and oxygen reduction reactions catalyzed by porphyrins and corroles.

  18. Non-Catalyzed Click Reactions of ADIBO Derivatives with 5-Methyluridine Azides and Conformational Study of the Resulting Triazoles (United States)

    Smyslova, Petra; Popa, Igor; Lyčka, Antonín; Tejral, Gracian; Hlavac, Jan


    Copper-free click reactions between a dibenzoazocine derivative and azides derived from 5-methyluridine were investigated. The non-catalyzed reaction yielded both regioisomers in an approximately equivalent ratio. The NMR spectra of each regioisomer revealed conformational isomery. The ratio of isomers was dependent on the type of regioisomer and the type of solvent. The synthesis of various analogs, a detailed NMR study and computational modeling provided evidence that the isomery was dependent on the interaction of the azocine and pyrimidine parts. PMID:26673606

  19. Iron-Catalyzed Reaction of Urea with Alcohols and Amines: A Safe Alternative for the Synthesis of Primary Carbamates. (United States)

    Peña-López, Miguel; Neumann, Helfried; Beller, Matthias


    A general study of the iron-catalyzed reaction of urea with nucleophiles is here presented. The carbamoylation of alcohols allows for the synthesis of N-unsubstituted (primary) carbamates, including present drugs (Felbamate and Meprobamate), without the necessity to apply phosgene and related derivatives. Using amines as nucleophiles gave rise to the respective mono- and disubstituted ureas via selective transamidation reaction. These atom-economical transformations provide a direct and selective access to valuable compounds from cheap and readily available urea using a simple Lewis-acidic iron(II) catalyst. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Rhodium-Catalyzed Insertion Reaction of PhP Group of Pentaphenylcyclopentaphosphine with Acyclic and Cyclic Disulfides. (United States)

    Arisawa, Mieko; Sawahata, Kyosuke; Yamada, Tomoki; Sarkar, Debayan; Yamaguchi, Masahiko


    Organophosphorus compounds with a phosphorus atom attached to a phenyl group and two organothio/organoseleno groups were synthesized using the rhodium-catalyzed insertion reaction of the PhP group of pentaphenylcyclopentaphosphine (PhP) 5 with acyclic disulfides and diselenides. The method was applied to the synthesis of heterocyclic compounds containing the S-P-S group by the reaction of (PhP) 5 and cyclic disulfides such as 1,2-dithietes, 1,2-dithiocane, 1,4,5-dithiopane, and 1,2-dithiolanes.

  1. Silylium ion-catalyzed challenging Diels-Alder reactions: the danger of hidden proton catalysis with strong Lewis acids. (United States)

    Schmidt, Ruth K; Müther, Kristine; Mück-Lichtenfeld, Christian; Grimme, Stefan; Oestreich, Martin


    The pronounced Lewis acidity of tricoordinate silicon cations brings about unusual reactivity in Lewis acid catalysis. The downside of catalysis with strong Lewis acids is, though, that these do have the potential to mediate the formation of protons by various mechanisms, and the thus released Brønsted acid might even outcompete the Lewis acid as the true catalyst. That is an often ignored point. One way of eliminating a hidden proton-catalyzed pathway is to add a proton scavenger. The low-temperature Diels-Alder reactions catalyzed by our ferrocene-stabilized silicon cation are such a case where the possibility of proton catalysis must be meticulously examined. Addition of the common hindered base 2,6-di-tert-butylpyridine resulted, however, in slow decomposition along with formation of the corresponding pyridinium ion. Quantitative deprotonation of the silicon cation was observed with more basic (Mes)(3)P to yield the phosphonium ion. A deuterium-labeling experiment verified that the proton is abstracted from the ferrocene backbone. A reasonable mechanism of the proton formation is proposed on the basis of quantum-chemical calculations. This is, admittedly, a particular case but suggests that the use of proton scavengers must be carefully scrutinized, as proton formation might be provoked rather than prevented. Proton-catalyzed Diels-Alder reactions are not well-documented in the literature, and a representative survey employing TfOH is included here. The outcome of these catalyses is compared with our silylium ion-catalyzed Diels-Alder reactions, thereby clearly corroborating that hidden Brønsted acid catalysis is not operating with our Lewis acid. Several simple-looking but challenging Diels-Alder reactions with exceptionally rare dienophile/enophile combinations are reported. Another indication is obtained from the chemoselectivity of the catalyses. The silylium ion-catalyzed Diels-Alder reaction is general with regard to the oxidation level of the

  2. Reaction mechanism of WGS and PROX reactions catalyzed by Pt/oxide catalysts revealed by an FeO(111)/Pt(111) inverse model catalyst. (United States)

    Xu, Lingshun; Wu, Zongfang; Jin, Yuekang; Ma, Yunsheng; Huang, Weixin


    We have employed XPS and TDS to study the adsorption and surface reactions of H2O, CO and HCOOH on an FeO(111)/Pt(111) inverse model catalyst. The FeO(111)-Pt(111) interface of the FeO(111)/Pt(111) inverse model catalyst exposes coordination-unsaturated Fe(II) cations (Fe(II)CUS) and the Fe(II)CUS cations are capable of modifying the reactivity of neighbouring Pt sites. Water facilely dissociates on the Fe(II)CUS cations at the FeO(111)-Pt(111) interface to form hydroxyls that react to form both water and H2 upon heating. Hydroxyls on the Fe(II)CUS cations can react with CO(a) on the neighbouring Pt(111) sites to produce CO2 at low temperatures. Hydroxyls act as the co-catalyst in the CO oxidation by hydroxyls to CO2 (PROX reaction), while they act as one of the reactants in the CO oxidation by hydroxyls to CO2 and H2 (WGS reaction), and the recombinative reaction of hydroxyls to produce H2 is the rate-limiting step in the WGS reaction. A comparison of reaction behaviors between the interfacial CO(a) + OH reaction and the formate decomposition reaction suggest that formate is the likely surface intermediate of the CO(a) + OH reaction. These results provide some solid experimental evidence for the associative reaction mechanism of WGS and PROX reactions catalyzed by Pt/oxide catalysts.

  3. Identification of the rate‐limiting step of the peroxygenase reactions catalyzed by the thermophilic cytochrome P450 from Sulfolobus tokodaii strain 7

    National Research Council Canada - National Science Library

    Hayakawa, Shohei; Matsumura, Hirotoshi; Nakamura, Nobuhumi; Yohda, Masafumi; Ohno, Hiroyuki


    Cytochrome P450 from the thermoacidophilic crenarchaeon Sulfolobus tokodaii strain 7 (P450st) is a thermophilic cytochrome P450 that shows high tolerance of harsh conditions and is capable of catalyzing some peroxygenase reactions...

  4. Efficient Boron-Copper Additions to Aryl-Substituted Alkenes Promoted by NHC–Based Catalysts. Enantioselective Cu-Catalyzed Hydroboration Reactions


    Lee, Yunmi; Hoveyda, Amir H.


    A Cu-catalyzed method for efficient boron-copper addition processes involving acyclic and cyclic disubstituted aryl olefins are reported. Reactions are promoted with 0.5–5 mol % of a readily available N-heterocyclic carbene (NHC) complex; the presence of MeOH promotes in situ protonation of the C–Cu bond and leads to efficient catalyst turnover, constituting a net Cu-catalyzed hydroboration process. Reactions proceed in >98:

  5. Kinetic and thermodynamic study of the reaction catalyzed by glucose-6-phosphate dehydrogenase with nicotinamide adenine dinucleotide

    Energy Technology Data Exchange (ETDEWEB)

    Martin del Campo, Julia S. [Departamento de Fisica Aplicada, Centro de Investigacion y de Estudios Avanzados - Unidad Merida, Carretera antigua a Progreso Km. 6, A.P. 73 Cordemex, 97310, Merida, Yucatan (Mexico); Patino, Rodrigo, E-mail: [Departamento de Fisica Aplicada, Centro de Investigacion y de Estudios Avanzados - Unidad Merida, Carretera antigua a Progreso Km. 6, A.P. 73 Cordemex, 97310, Merida, Yucatan (Mexico)


    Research highlights: {yields} The reaction catalyzed by one enzyme of the pentose phosphate pathway was studied. {yields} A spectrophotometric method is proposed for kinetic and thermodynamic analysis. {yields} The pH and the temperature influences are reported on physical chemical properties. {yields} Relative concentrations of substrates are also important in the catalytic process. - Abstract: The enzyme glucose-6-phosphate dehydrogenase (G6PD, EC from Leuconostoc mesenteroides has a dual coenzyme specificity with oxidized nicotinamide adenine dinucleotide (NAD{sub ox}) and oxidized nicotinamide adenine dinucleotide phosphate as electron acceptors. The G6PD coenzyme selection is determined by the metabolic cellular prevailing conditions. In this study a kinetic and thermodynamic analysis is presented for the reaction catalyzed by G6PD from L. mesenteroides with NAD{sub ox} as coenzyme in phosphate buffer. For this work, an in situ spectrophotometric technique was employed based on the detection of one product of the reaction. Substrate and coenzyme concentrations as well as temperature and pH effects were evaluated. The apparent equilibrium constant, the Michaelis constant, and the turnover number were determined as a function of each experimental condition. The standard transformed Gibbs energy of reaction was determined from equilibrium constants at different initial conditions. For the product 6-phospho-D-glucono-1,5-lactone, a value of the standard Gibbs energy of formation is proposed, {Delta}{sub f}G{sup o} = -1784 {+-} 5 kJ mol{sup -1}.

  6. Nickel-Catalyzed Decarbonylative Silylation, Borylation, and Amination of Arylamides via a Deamidative Reaction Pathway

    KAUST Repository

    Rueping, Magnus


    A nickel-catalyzed decarbonylative silylation, borylation, and amination of amides has been developed. This new methodology allows the direct interconversion of amides to arylsilanes, arylboronates, and arylamines and enables a facile route for carbon–heteroatom bond formations in a straightforward and mild fashion.

  7. Beta-D-xylosidase from Selenomonas ruminantium: thermodynamics of enzyme-catalyzed and noncatalyzed reactions (United States)

    Beta-D-xylosidase/alpha-L-arabinofuranosidase from Selenomonas ruminantium (SXA) is the most active enzyme known for catalyzing hydrolysis of 1,4-beta-D-xylooligosaccharides to D-xylose. Temperature dependence for hydrolysis of 4-nitrophenyl-beta-D-xylopyranoside (4NPX), 4-nitrophenyl-alpha-L-arabi...

  8. Optimizing Metalloporphyrin-Catalyzed Reduction Reactions for In Situ Remediation of DOE Contaminants

    Energy Technology Data Exchange (ETDEWEB)

    Schlautman, Mark A. [Clemson University, Clemson, SC (United States)


    Past activities have resulted in a legacy of contaminated soil and groundwater at Department of Energy facilities nationwide. Uranium and chromium are among the most frequently encountered and highest-priority metal and radionuclide contaminants at DOE installations. Abiotic chemical reduction of uranium and chromium at contaminated DOE sites can be beneficial because the reduced metal species are less soluble in water, less mobile in the environment, and less toxic to humans and ecosystems. Although direct biological reduction has been reported for U(VI) and Cr(VI) in laboratory studies and at some field sites, the reactions can sometimes be slow or even inhibited due to unfavorable environmental conditions. One promising approach for the in-situ remediation of DOE contaminants is to develop electron shuttle catalysts that can be delivered precisely to the specific subsurface locations where contaminants reside. Previous research has shown that reduction of oxidized organic and inorganic contaminants often can be catalyzed by electron shuttle systems. Metalloporphyrins and their derivatives are well known electron shuttles for many biogeochemical systems, and thus were selected to study their catalytic capabilities for the reduction of chromium and uranium in the presence of reducing agents. Zero valent iron (ZVI) was chosen as the primary electron donor in most experimental systems. Research proceeded in three phases and the key findings of each phase are reported here. Phase I examined Cr(VI) reduction and utilized micro- and nano-sized ZVI as the electron donors. Electron shuttle catalysts tested were cobalt- and iron-containing metalloporphyrins and Vitamin B12. To aid in the recycle and reuse of the nano-sized ZVI and soluble catalysts, sol-gels and calcium-alginate gel beads were tested as immobilization/support matrices. Although the nano-sized ZVI could be incorporated within the alginate gel beads, preliminary attempts to trap it in sol-gels were not

  9. Palladium-catalyzed direct arylation of azine and azole N-oxides: reaction development, scope and applications in synthesis. (United States)

    Campeau, Louis-Charles; Stuart, David R; Leclerc, Jean-Philippe; Bertrand-Laperle, Mégan; Villemure, Elisia; Sun, Ho-Yan; Lasserre, Sandrine; Guimond, Nicolas; Lecavallier, Melanie; Fagnou, Keith


    Palladium-catalyzed direct arylation reactions are described with a broad range of azine and azole N-oxides. In addition to aspects of functional group compatibility, issues of regioselectivity have been explored when nonsymmetrical azine N-oxides are used. In these cases, both the choice of ligand and the nature of the azine substituents play important roles in determining the regioisomeric distribution. When azole N-oxides are employed, preferential reaction is observed for arylation at C2 which occurs under very mild conditions. Subsequent reactions are observed to occur at C5 followed by arylation at C4. The potential utility of this methodology is illustrated by its use in the synthesis of a potent sodium channel inhibitor 1 and a Tie2 Tyrosine Kinase inhibitor 2.

  10. A thermodynamic study of ketoreductase-catalyzed reactions 4. Reduction of 2-substituted cyclohexanones in n-hexane

    Energy Technology Data Exchange (ETDEWEB)

    Tewari, Yadu B. [Biochemical Science Division and Analytical Chemistry Division, National Institute of Standards and Technology, Gaithersburg, MD 20899 (United States)]. E-mail:; Liebman, Joel F. [Department of Chemistry and Biochemistry, University of Maryland, Baltimore County, Baltimore, MD 21250 (United States)]. E-mail:; Rozzell, J. David [BioCatalytics, Inc., 129 N. Hill Avenue, Pasadena, CA 91106 (United States)]. E-mail:; Vanderah, David J. [Biochemical Science Division and Analytical Chemistry Division, National Institute of Standards and Technology, Gaithersburg, MD 20899 (United States)]. E-mail:; Schantz, Michele M. [Biochemical Science Division and Analytical Chemistry Division, National Institute of Standards and Technology, Gaithersburg, MD 20899 (United States)]. E-mail:


    The equilibrium constants K for the ketoreductase-catalyzed reduction reactions (2-substituted cyclohexanone+2-propanol=cis- and trans-2-substituted cyclohexanol+acetone) have been measured in n-hexane as solvent. The 2-substituted cyclohexanones included in this study are: 2-methylcyclohexanone, 2-phenylcyclohexanone, and 2-benzylcyclohexanone. The equilibrium constants K for the reactions with 2-methylcyclohexanone were measured over the range T=288.15 to 308.05K. The thermodynamic quantities at T=298.15K are: K=(2.13+/-0.06); {delta}{sub r}G{sub m}{sup o}=-(1.87+/-0.06)kJ.mol{sup -1}; {delta}{sub r}H{sub m}{sup o}=-(6.56+/-2.68)kJ.mol{sup -1}; and {delta}{sub r}S{sub m}{sup o}=-(15.7+/-9.2)J.K{sup -1}.mol{sup -1} for the reaction involving cis-2-methylcyclohexanol, and K=(10.7+/-0.2); {delta}{sub r}G{sub m}{sup o}=-(5.87+/-0.04)kJ.mol{sup -1}; {delta}{sub r}H{sub m}{sup o}=-(2.54+/-1.8)kJ.mol{sup -1}; and {delta}{sub r}S{sub m}{sup o}=(11.2+/-6.4)J.K{sup -1}.mol{sup -1} for the reaction involving trans-2-methylcyclohexanol. The standard molar Gibbs free energy changes {delta}{sub r}G{sub m}{sup o} for the reactions (trans-2-substituted cyclohexanol=cis-2-substituted cyclohexanol) in n-hexane have also been calculated and compared with the literature data that pertain to reactions in the gas phase and at higher temperatures. Experiments carried out with a chiral column demonstrated that the enzymatic reduction of 2-phenylcyclohexanone catalyzed by the ketoreductase used in this study is not stereoselective.

  11. Steady state kinetic evidence for an acyl-enzyme intermediate in reactions catalyzed by bovine spleen cathepsin B. (United States)

    Bajkowski, A S; Frankfater, A


    Cathepsin B from bovine spleen was shown to catalyze transacylation reactions between esters of N-substituted amino acids and nucleophiles. These reactions appeared to proceed through an intermediate between cathepsin B and the acyl portion of the substrate. Of the various nucleophiles tested, dipeptides were found to be the most effective acyl group acceptors. A method was devised for calculating the acylation and deacylation rate constants from increases in the maximum velocity of disappearance of the substrate with increasing concentrations of the nucleophile. The values for the second order rate constants for the reaction of the acyl-enzyme with the nucleophile, k4, were found to depend on the identity of the dipeptide, while the first order rate constants for formation and hydrolysis of the acyl-enzyme, k2 and k3, were dipeptide-independent. With N alpha-benzyloxycarbonyl-L-lysine p-nitrophenyl ester at pH 6.5, k2 and k3 were found to be 360 s-1 and 6.6 s-1, respectively, indicating that the deacylation step was rate-determining for the hydrolysis of this substrate. In contrast, dipeptide nucleophiles did not significantly accelerate the cathepsin B-catalyzed cleavage of either the p-nitroanilide or the 2-naphthylamide of N alpha-benzoylarginine, suggesting that the hydrolysis of these amide substrates was acylation rate-limiting. These findings support the suggestion that cathepsin B is mechanistically similar to the cysteine proteinase papain.

  12. Bulk gold catalyzed oxidation reactions of amines and isocyanides and iron porphyrin catalyzed N-H and O-H bond insertion/cyclization reactions of diamines and aminoalcohols

    Energy Technology Data Exchange (ETDEWEB)

    Klobukowski, Erik [Iowa State Univ., Ames, IA (United States)


    This work involves two projects. The first project entails the study of bulk gold as a catalyst in oxidation reactions of isocyanides and amines. The main goal of this project was to study the activation and reactions of molecules at metal surfaces in order to assess how organometallic principles for homogeneous processes apply to heterogeneous catalysis. Since previous work had used oxygen as an oxidant in bulk gold catalyzed reactions, the generality of gold catalysis with other oxidants was examined. Amine N-oxides were chosen for study, due to their properties and use in the oxidation of carbonyl ligands in organometallic complexes. When amine N-oxides were used as an oxidant in the reaction of isocyanides with amines, the system was able to produce ureas from a variety of isocyanides, amines, and amine N-oxides. In addition, the rate was found to generally increase as the amine N-oxide concentration increased, and decrease with increased concentrations of the amine. Mechanistic studies revealed that the reaction likely involves transfer of an oxygen atom from the amine N-oxide to the adsorbed isocyanide to generate an isocyanate intermediate. Subsequent nucleophilic attack by the amine yields the urea. This is in contrast to the bulk gold-catalyzed reaction mechanism of isocyanides with amines and oxygen. Formation of urea in this case was proposed to proceed through a diaminocarbene intermediate. Moreover, formation of the proposed isocyanate intermediate is consistent with the reactions of metal carbonyl ligands, which are isoelectronic to isocyanides. Nucleophilic attack at coordinated CO by amine N-oxides produces CO{sub 2} and is analogous to the production of an isocyanate in this gold system. When the bulk gold-catalyzed oxidative dehydrogenation of amines was examined with amine N-oxides, the same products were afforded as when O{sub 2} was used as the oxidant. When the two types of oxidants were directly compared using the same reaction system and

  13. Synthesis of chiral biphenol-based diphosphonite ligands and their application in palladium-catalyzed intermolecular asymmetric allylic amination reactions. (United States)

    Shi, Ce; Chien, Chih-Wei; Ojima, Iwao


    A library of new 2,2'-bis(diphenylphosphinoyloxy)-1,1'-binaphthyl (binapo)-type chiral diphosphonite ligands was designed and synthesized based on chiral 3,3',5,5',6,6'-hexasubstituted biphenols. These bop ligands have exhibited excellent efficiency in a palladium-catalyzed intermolecular allylic amination reaction, which provides a key intermediate for the total synthesis of Strychnos indole alkaloids with enantiopurities of up to 96% ee. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Acid-, base-, and lewis-acid-catalyzed heterolysis of methoxide from an alpha-hydroxy-beta-methoxy radical: models for reactions catalyzed by coenzyme B12-dependent diol dehydratase. (United States)

    Xu, Libin; Newcomb, Martin


    [Reaction: see text].A model for glycol radicals was employed in laser flash photolysis kinetic studies of catalysis of the fragmentation of a methoxy group adjacent to an alpha-hydroxy radical center. Photolysis of a phenylselenylmethylcyclopropane precursor gave a cyclopropylcarbinyl radical that rapidly ring opened to the target alpha-hydroxy-beta-methoxy radical (3). Heterolysis of the methoxy group in 3 gave an enolyl radical (4a) or an enol ether radical cation (4b), depending upon pH. Radicals 4 contain a 2,2-diphenylcyclopropane reporter group, and they rapidly opened to give UV-observable diphenylalkyl radicals as the final products. No heterolysis was observed for radical 3 under neutral conditions. In basic aqueous acetonitrile solutions, specific base catalysis of the heterolysis was observed; the pK(a) of radical 3 was determined to be 12.5 from kinetic titration plots, and the ketyl radical formed by deprotonation of 3 eliminated methoxide with a rate constant of 5 x 10(7) s(-1). In the presence of carboxylic acids in acetonitrile solutions, radical 3 eliminated methanol in a general acid-catalyzed reaction, and rate constants for protonation of the methoxy group in 3 by several acids were measured. Radical 3 also reacted by fragmentation of methoxide in Lewis-acid-catalyzed heterolysis reactions; ZnBr2, Sc(OTf)3, and BF3 were found to be efficient catalysts. Catalytic rate constants for the heterolysis reactions were in the range of 3 x 10(4) to 2 x 10(6) s(-1). The Lewis-acid-catalyzed heterolysis reactions are fast enough for kinetic competence in coenzyme B12 dependent enzyme-catalyzed reactions of glycols, and Lewis-acid-catalyzed cleavages of beta-ethers in radicals might be applied in synthetic reactions.

  15. Kinetic study for the ethanolysis of fish oil catalyzed by lipozyme(®) 435 in different reaction media. (United States)

    Bucio, Silvia Liliana; Solaesa, Ángela García; Sanz, María Teresa; Melgosa, Rodrigo; Beltrán, Sagrario; Sovová, Helena


    The ethanolysis of fish oil in various reaction medium (tert-pentanol, n-hexane and solvent free system) catalyzed by the immobilized commercial lipase Lipozyme(®) 435 (Candida Antarctica) at atmospheric pressure has been studied in this work. The effect of some kinetic parameters, such as the amount of lipase, temperature and the initial reactant molar ratio ethanol:oil on monoacyglyceride and ethyl ester yield has been analyzed. Experimental data were successfully correlated by a simple kinetic model based on the elementary reactions proposed in this work. At high initial reactant molar ratio the three elementary steps can be considered as irreversible. However the reaction rate constants ratio for the deacylation of monoglyceride to glycerol decreased by decreasing the molar ratio ethanol:oil. The reaction rates are slower in n-hexane as reaction medium compared to tert-pentanol and a solvent-free system, at the experimental conditions essayed in this work. In this last case, ethanol acts as solvent for reaction and as reactant.

  16. Mechanistic investigation inspired "on water" reaction for hydrobromic acid-catalyzed Friedel-Crafts-type reaction of β-naphthol and formaldehyde. (United States)

    Cao, Shanshan; Yuan, Haiyan; Yang, Yang; Wang, Mang; Zhang, Xiaoying; Zhang, Jingping


    The mechanism of the HBr-catalyzed Friedel-Crafts-type reaction between β-naphthol and HCHO was investigated by DFT to improve this reaction. The HBr-H2 O co-catalyzed the preferential pathway undergoes the concerted nucleophilic addition and hydrogen shift, stepwise followed by H2 O elimination and the CC bond formation. The origin of the high catalytic activity of HBr is ascribed to CH···Br- and OH···Br- interactions, which suggest that the active species is Br- . Moreover, water molecules efficiently assist in improving the activity of Br- . The computational results show that solvent polarity profoundly affects the activation barriers. To our delight, the activation barrier of the rate-determining step for the favored pathway in water is comparable (0.6 kcal/mol difference) with that in acetonitrile. The experimental observation further confirmed our results and demonstrated that the title reaction can be successfully achieved "on water." Therefore, we open a new efficient and green strategy for the synthesis of biphenol derivatives. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

  17. Increased yield of β-glucosidase-catalyzed hydrolysis reactions in the presence of betaine-type metabolite analog. (United States)

    Sehata, Shiro; Suzuki, Ryojun; Koumoto, Kazuya


    β-Glucosidases (EC, abundant enzymes distributed in animals, plants and microorganism, has been generating lots of attentions for bioethanol production from cellulosic biomass. In this study, using three different origins of β-glucosidases, glucose productivity of β-glucosidase-catalyzed hydrolysis reactions in the presence of synthetic betaine-type metabolite analog (2-N,N,N-tri-n-butylammonium) acetate, was investigated. By the addition of the analog, the hydrolysis yields for all β-glucosidases was highly improved from 4-13 to 64-100 %. To understand the factors affecting on the yield enhancements, the kinetic parameters, inhibition constants of end-product and temporal stability of β-glucosidases were compared. As a result, enhancement of the yields is mainly related to the increase in the temporal stability of β-glucosidases in the presence of the analog. The present findings lead to not only improve the glucose productivity of β-glucosidase-catalyzed hydrolysis reaction toward bioethanol production but also apply to a new stabilization method for various unstable enzymes.

  18. Switchable Diastereoselectivity in the Fluoride Promoted Vinylogous Mukaiyama-Michael Reaction of 2-Trimethylsilyloxyfuran Catalyzed by Crown Ethers

    KAUST Repository

    Della Sala, Giorgio


    The fluoride promoted vinylogous Mukaiyama-Michael reaction (VMMR) of 2-trimethylsilyloxyfuran with diverse α,β-unsaturated ketones is described. The TBAF catalyzed VMMR afforded high anti-diastereoselectivity irrespective of the solvents used. The KF/crown ethers catalytic systems proved to be highly efficient in terms of yields and resulted in a highly diastereoselective unprecedented solvent/catalyst switchable reaction. Anti-adducts were obtained as single diastereomers or with excellent diastereoselectivities when benzo-15-crown-5 in CH2Cl2 was employed. On the other hand, high syn-diastereoselectivities (from 76:24 to 96:4) were achieved by employing dicyclohexane-18-crown-6 in toluene. Based on DFT calculations, the catalysts/solvents-dependent switchable diastereoselectivities are proposed to be the result of loose or tight cation-dienolate ion pairs.

  19. Twisted Amides: From Obscurity to Broadly Useful Transition-Metal-Catalyzed Reactions by N-C Amide Bond Activation. (United States)

    Liu, Chengwei; Szostak, Michal


    The concept of using amide bond distortion to modulate amidic resonance has been known for more than 75 years. Two classic twisted amides (bridged lactams) ingeniously designed and synthesized by Kirby and Stoltz to feature fully perpendicular amide bonds, and as a consequence emanate amino-ketone-like reactivity, are now routinely recognized in all organic chemistry textbooks. However, only recently the use of amide bond twist (distortion) has advanced to the general organic chemistry mainstream enabling a host of highly attractive N-C amide bond cross-coupling reactions of broad synthetic relevance. In this Minireview, we discuss recent progress in this area and present a detailed overview of the prominent role of amide bond destabilization as a driving force in the development of transition-metal-catalyzed cross-coupling reactions by N-C bond activation. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Synthesis of the copper chelator TGTA and evaluation of its ability to protect biomolecules from copper induced degradation during copper catalyzed azide-alkyne bioconjugation reactions. (United States)

    Ekholm, F S; Pynnönen, H; Vilkman, A; Koponen, J; Helin, J; Satomaa, T


    One of the most successful bioconjugation strategies to date is the copper(I)-catalyzed cycloaddition reaction (CuAAC), however, the typically applied reaction conditions have been found to degrade sensitive biomolecules. Herein, we present a water soluble copper chelator which can be utilized to protect biomolecules from copper induced degradation.

  1. Mechanistic Investigations of the Iron(III)-Catalyzed Carbonyl-Olefin Metathesis Reaction. (United States)

    Ludwig, Jacob R; Phan, Susan; McAtee, Christopher C; Zimmerman, Paul M; Devery, James J; Schindler, Corinna S


    Iron(III)-catalyzed carbonyl-olefin ring-closing metathesis represents a new approach toward the assembly of molecules traditionally generated by olefin-olefin metathesis or olefination. Herein, we report detailed synthetic, spectroscopic, kinetic, and computational studies to determine the mechanistic features imparted by iron(III), substrate, and temperature to the catalytic cycle. These data are consistent with an iron(III)-mediated asynchronous, concerted [2+2]-cycloaddition to form an intermediate oxetane as the turnover-limiting step. Fragmentation of the oxetane via Lewis acid-activation results in the formation of five- and six-membered unsaturated carbocycles.

  2. Cationic Pd(II-catalyzed C–H activation/cross-coupling reactions at room temperature: synthetic and mechanistic studies

    Directory of Open Access Journals (Sweden)

    Takashi Nishikata


    Full Text Available Cationic palladium(II complexes have been found to be highly reactive towards aromatic C–H activation of arylureas at room temperature. A commercially available catalyst [Pd(MeCN4](BF42 or a nitrile-free cationic palladium(II complex generated in situ from the reaction of Pd(OAc2 and HBF4, effectively catalyzes C–H activation/cross-coupling reactions between aryl iodides, arylboronic acids and acrylates under milder conditions than those previously reported. The nature of the directing group was found to be critical for achieving room temperature conditions, with the urea moiety the most effective in promoting facile coupling reactions at an ortho C–H position. This methodology has been utilized in a streamlined and efficient synthesis of boscalid, an agent produced on the kiloton scale annually and used to control a range of plant pathogens in broadacre and horticultural crops. Mechanistic investigations led to a proposed catalytic cycle involving three steps: (1 C–H activation to generate a cationic palladacycle; (2 reaction of the cationic palladacycle with an aryl iodide, arylboronic acid or acrylate, and (3 regeneration of the active cationic palladium catalyst. The reaction between a cationic palladium(II complex and arylurea allowed the formation and isolation of the corresponding palladacycle intermediate, characterized by X-ray analysis. Roles of various additives in the stepwise process have also been studied.

  3. Gold-nanoparticle-catalyzed synthesis of propargylamines: the traditional A3-multicomponent reaction performed as a two-step flow process. (United States)

    Abahmane, Lahbib; Köhler, J Michael; Gross, G Alexander


    The alkyne, aldehyde, amine A(3)-coupling reaction, a traditional multicomponent reaction (MCR), has been investigated as a two-step flow process. The implicated aminoalkylation reaction of phenylacetylene with appropriate aldimine intermediates was catalyzed by gold nanoparticles impregnated on alumina. The aldimine formation was catalyzed by Montmorillonite K10 beforehand. The performance of the process has been investigated with respect to different reaction regimes. Usually, the A(3)-multicomponent reaction is performed as a "one-pot" process. Diversity-oriented syntheses using MCRs often have the shortcoming that only low selectivity and low yields are achieved. We have used a flow-chemistry approach to perform the A(3)-MCR in a sequential manner. In this way, the reaction performance was significantly enhanced in terms of shortened reaction time, and the desired propargylamines were obtained in high yields. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Effect of water content and temperature on Carica papaya lipase catalyzed esterification and transesterification reactions

    Directory of Open Access Journals (Sweden)

    Turon Fabrice


    Full Text Available Temperature and water activity (a w of the reaction medium are two factors that govern enzyme reactions. We studied the influence of these two parameters on the esterification and transesterification activity of Carica papaya lipase in water and solvent free reactions. It was found that over the course of reaction the catalytic activity of C. papaya lipase was dependent on these factors. The best lipase activity for both reactions was at a temperature of 55°C and water activity of 0.22, which corresponds to 2 g of water per 100 g of C. papaya latex.

  5. The role of vanadium haloperoxidases in the formation of volatile brominated compounds and their impact on the environment

    NARCIS (Netherlands)

    Wever, R.; van der Horst, M.A.


    Vanadium haloperoxidases differ strongly from heme peroxidases in substrate specificity and stability and in contrast to a heme group they contain the bare metal oxide vanadate as a prosthetic group. These enzymes specifically oxidize halides in the presence of hydrogen peroxide into hypohalous

  6. Ultrasound assisted lipase catalyzed synthesis of cinnamyl acetate via transesterification reaction in a solvent free medium. (United States)

    Tomke, Prerana D; Rathod, Virendra K


    Cinnamyl acetate is known for its use as flavor and fragrance material in different industries such as food, pharmaceutical, cosmetic etc. This work focuses on ultrasound assisted lipase (Novozym 435) catalyzed synthesis of cinnamyl acetate via transesterification of cinnamyl alcohol and vinyl acetate in non-aqueous, solvent free system. Optimization of various parameters shows that a higher yield of 99.99% can be obtained at cinnamyl alcohol to vinyl acetate ratio of 1:2 with 0.2% of catalyst, at 40°C and 150 rpm, with lower ultrasound power input of 50 W (Ultrasound intensity 0.81 W/cm(2)), at 25 kHz frequency, 50% duty cycle. Further, the time required for the maximum conversion is reduced to 20 min as compared to 60 min of conventional process. Similarly, the enzyme can be successfully reused seven times without loss of enzyme activity. Thus, ultrasound helps to enhance the enzyme catalyzed synthesis of flavors. Copyright © 2015 Elsevier B.V. All rights reserved.

  7. The Nature of Acid-Catalyzed Acetalization Reaction of 1,2-Propylene Glycol and Acetaldehyde

    Energy Technology Data Exchange (ETDEWEB)

    Cheng, Chen; Chen, Hui; Li, Xia; Hu, Jianli; Liang, Baochen [Tianjin University of Technology, Tianjin (China)


    We investigated catalytic activity of ion-exchange resins in acetalization of 1,2-propylene glycol with acetaldehyde. The impacts of reaction variables, such as temperature, reaction time, catalyst loading and feedstock composition, on the conversion of 1,2-propylene glycol were measured. The life of the catalyst was also studied. Furthermore, the reaction kinetics of 1,2-propylene glycol acetalization was studied. It was found that reaction rate followed the first order kinetics to acetaldehyde and 1,2-propylene glycol, respectively. Therefore, overall acetalization reaction should follow the second-order reaction kinetics, expressed as r - kC{sup nA}{sub A}C{sup nB}{sub B} = 19.74e{sup -650/T}C{sup 1}{sub A}C{sup 1}{sub B}.

  8. Design, synthesis, and applications of potential substitutes of t-Bu-phosphinooxazoline in Pd-catalyzed asymmetric transformations and their use for the improvement of the enantioselectivity in the Pd-catalyzed allylation reaction of fluorinated allyl enol carbonates. (United States)

    Bélanger, Étienne; Pouliot, Marie-France; Courtemanche, Marc-André; Paquin, Jean-François


    The design, synthesis, and applications of potential substitutes of t-Bu-PHOX in asymmetric catalysis is reported. The design relies on the incorporation of geminal substituents at C5 in combination with a substituent at C4 other than t-butyl (i-Pr, i-Bu, or s-Bu). Most of these new members of the PHOX ligand family behave similarly in terms of stereoinduction to t-Bu-PHOX in three palladium-catalyzed asymmetric transformations. Electronically modified ligands were also prepared and used to improve the enantioselectivity in the Pd-catalyzed allylation reaction of fluorinated allyl enol carbonates.

  9. Red seaweed enzyme-catalyzed bromination of bromophenol red: An inquiry-based kinetics laboratory experiment for undergraduates. (United States)

    Jittam, Piyachat; Boonsiri, Patcharee; Promptmas, Chamras; Sriwattanarothai, Namkang; Archavarungson, Nattinee; Ruenwongsa, Pintip; Panijpan, Bhinyo


    Haloperoxidase enzymes are of interest for basic and applied bioscientists because of their increasing importance in pharmaceutical industry and environmental cleanups. In a guided inquiry-based laboratory experiment for life-science, agricultural science, and health science undergraduates, the bromoperoxidase from a red seaweed was used to brominate bromophenol red, a novel starting substrate. Substrate and enzyme concentration dependence of this enzyme-catalyzed reaction as followed colorimetrically yielded initial rates of reaction that the students compared with those of their peers. The students worked as collaborative groups partially designing their own experiments and carrying them out. In performing the laboratory experiment, they were minimally guided by the instructor and teaching assistants. To engage the students before the laboratory, a short activity involving the enzyme-induced color change was carried out. At the end of the laboratory session, student groups discussed their results in front of the class and reached their own conclusions. Most students had better understanding of important concepts in enzyme kinetics and showed good attitude toward the overall student-centered laboratory exercise. Copyright © 2009 International Union of Biochemistry and Molecular Biology, Inc.

  10. Mechanism of the reaction catalyzed by mandelate racemase. 1. Chemical and kinetic evidence for a two-base mechanism

    Energy Technology Data Exchange (ETDEWEB)

    Powers, V.M.; Koo, C.W.; Kenyon, G.L. (Univ. of California, San Francisco (United States)); Gerlt, J.A.; Kozarich, J.W. (Univ. of Maryland, College Park (United States))


    The fate of the {alpha}-hydrogen of mandelate in the reaction catalyzed by mandelate racemase has been investigated by a mass spectroscopic method. The method entails the incubation of (R)- or (S)-({alpha}-{sup 1}H) mandelate in buffered D{sub 2}O to a low extent of turnover (about 5-8%), esterification of the resulting mixture of mandelates with diazomethane, derivatization of the methyl esters with a chiral derivatizing agent, and quantitation of the isotope content of the {alpha}-hydrogen of both substrate and product by gas chromatography/mass spectrometric analysis. No significant substrate-derived {alpha}-protium was found in the product for racemization in either direction. In addition, in the (R) to (S) direction almost no exchange of the {alpha}-hydrogen in the remaining (R) substrate pool occurred, but in the (S) to (R) direction 3.5-5.1% exchange of the {alpha}-hydrogen in the remaining substrate (after 5.1-7.2% net turnover) was found. Qualitatively similar results were obtained in the (S) to (R) direction in H{sub 2}O when (S)-({alpha}-{sup 2}H)mandelate was used as substrate. In other experiments, an overshoot in the progress curve was observed when the racemization of either enantiomer of ({alpha}-{sup 1}H) mandelate in D{sub 2}O was monitored by following the change in ellipticity of the reaction mixture; the magnitude of the overshoot was greater in the (R) to (S) than in the (S) to (R) direction. All of the available data indicate that the reaction catalyzed by mandelate racemase proceeds by a two-base mechanism, in contrast to earlier proposals.

  11. Cobalt catalyzed peroxymonosulfate oxidation of tetrabromobisphenol A: Kinetics, reaction pathways, and formation of brominated by-products

    Energy Technology Data Exchange (ETDEWEB)

    Ji, Yuefei [Department of Environmental Science and Engineering, Nanjing Agricultural University, Nanjing 210095 (China); Kong, Deyang [Nanjing Institute of Environmental Science, Ministry of Environmental Protection of PRC, Nanjing 210042 (China); Lu, Junhe, E-mail: [Department of Environmental Science and Engineering, Nanjing Agricultural University, Nanjing 210095 (China); Jin, Hao; Kang, Fuxing; Yin, Xiaoming; Zhou, Quansuo [Department of Environmental Science and Engineering, Nanjing Agricultural University, Nanjing 210095 (China)


    Highlights: • Cobalt catalyzed peroxymonosulfate oxidation of tetrabromobisphenol A. • Phenolic moiety was the reactive site for sulfate radical attack. • Pathways include β-scission, oxidation, debromination and coupling reactions. • Brominated disinfection by-products were found during TBBPA degradation. • Humic acid inhibited TBBPA degradation but promoted DBPs formation. - Abstract: Degradation of tetrabromobisphenol A (TBBPA), a flame retardant widely spread in the environment, in Co(II) catalyzed peroxymonosulfate (PMS) oxidation process was systematically explored. The second-order-rate constant for reaction of sulfate radical (SO{sub 4}{sup ·−}) with TBBPA was determined to be 5.27 × 10{sup 10} M{sup −1} s{sup −1}. Apparently, degradation of TBBPA showed first-order kinetics to the concentrations of both Co(II) and PMS. The presence of humic acid (HA) and bicarbonate inhibited TBBPA degradation, most likely due to their competition for SO{sub 4}{sup ·−}. Degradation of TBBPA was initiated by an electron abstraction from one of the phenolic rings. Detailed transformation pathways were proposed, including β-scission of isopropyl bridge, phenolic ring oxidation, debromination and coupling reactions. Further oxidative degradation of intermediates in Co(II)/PMS process yielded brominated disinfection by-products (Br-DBPs) such as bromoform and brominated acetic acids. Evolution profile of Br-DBPs showed an initially increasing and then decreasing pattern with maximum concentrations occurring around 6–10 h. The presence of HA enhanced the formation of Br-DBPs significantly. These findings reveal potentially important, but previously unrecognized, formation of Br-DBPs during sulfate radical-based oxidation of bromide-containing organic compounds that may pose toxicological risks to human health.

  12. Refined transition-state models for proline-catalyzed asymmetric Michael reactions under basic and base-free conditions. (United States)

    Sharma, Akhilesh K; Sunoj, Raghavan B


    The stereocontrolling transition state (TS) models for C-C bond formation relying on hydrogen bonding have generally been successful in proline-catalyzed aldol, Mannich, α-amination, and α-aminoxylation reactions. However, the suitability of the hydrogen-bonding model in protic and aprotic conditions as well as under basic and base-free conditions has not been well established for Michael reactions. Through a comprehensive density functional theory investigation, we herein analyze different TS models for the stereocontrolling C-C bond formation, both in the presence and absence of a base in an aprotic solvent (THF). A refined stereocontrolling TS for the Michael reaction between cyclohexanone and nitrostyrene is proposed. The new TS devoid of hydrogen bonding between the nitro group of nitrostyrene and carboxylic acid of proline, under base-free conditions, is found to be more preferred over the conventional hydrogen-bonding model besides being able to reproduce the experimentally observed stereochemical outcome. A DBU-bound TS is identified as more suitable for rationalizing the origin of asymmetric induction under basic reaction conditions. In both cases, the most preferred approach of nitrostyrene is identified as occurring from the face anti to the carboxylic acid of proline-enamine. The predicted enantio- and diastereoselectivities are in very good agreement with the experimental observations.

  13. Bulky Monodentate Phosphoramidites in Palladium-Catalyzed Allylic Alkylation Reactions : Aspects of Regioselectivity and Enantioselectivity

    NARCIS (Netherlands)

    Boele, Maarten D.K.; Kamer, Paul C.J.; Lutz, Martin; Spek, Anthony L.; Vries, Johannes G. de; Leeuwen, Piet W.N.M. van; Strijdonck, Gino P.F. van


    A series of bulky monodentate phosphoramidite ligands, based on biphenol, BINOL and TADDOL backbones, have been employed in the Pd-catalysed allylic alkylation reaction. Reaction of disodium diethyl 2-methyl malonate with monosubstituted allylic substrates in the presence of palladium complexes of

  14. B (C 6 F 5) 3 catalyzed one-pot three-component Biginelli reaction ...

    Indian Academy of Sciences (India)

    The main highlights of the present protocol is low catalyst loading, low toxicity, compatibility with acid-labile-protecting groups, short reaction time, consistently excellent yields and simple reaction/workup procedure. Moreover, the applicability of the present methodology for large-scale synthesis of monastrol highlights its ...

  15. Asymmetric Aldol Reaction Catalyzed by L-Proline and Achiral Thiourea Fluoroboric Acid Salt

    Energy Technology Data Exchange (ETDEWEB)

    Cho, Eun; Lee, Haney; Kim, Taek Hyeon [Chonnam National University, Gwangju (Korea, Republic of)


    Considering its ready availability and low cost, L-proline would be the first choice catalyst for preparing aldol adducts with high diastereo- and enantioselectivity. However, proline presents some major drawbacks, including poor performance in direct aldol reactions with aromatic aldehydes, limited solubility, and reactivity in nonpolar organic solvents, and side reactions that make using high catalyst loadings necessary to reach satisfactory conversions. Therefore, numerous proline-modified organo catalysts such as prolinamides, proline thioamides, sulfonamides, chiral amines, and organic salts have been designed for direct aldol reactions. An alternative is to add a readily available additive to the reactions containing proline. This last approach is clearly advantageous in avoiding tedious chemical syntheses of organo catalysts and would ultimately allow the construction of libraries of catalyst protocols by simply changing the additive. Acid additives can influence the outcome of enamine mediated reactions; however, only a few screening studies of acid additions to thiourea organo catalysts are available in the literature. The reaction between cyclohexanone and 4-nitrobenzaldehyde was selected as a standard model reaction for screening of more effective acid additives to thiourea.

  16. Monitoring mass transport in heterogeneously catalyzed reactions by field-gradient NMR for assessing reaction efficiency in a single pellet. (United States)

    Buljubasich, L; Blümich, B; Stapf, S


    An important aspect in assessing the performance of a catalytically active reactor is the accessibility of the reactive sites inside the individual pellets, and the mass transfer of reactants and products to and from these sites. Optimal design often requires a suitable combination of micro- and macropores in order to facilitate mass transport inside the pellet. In an exothermic reaction, fluid exchange between the pellet and the surrounding medium is enhanced by convection, and often by the occurrence of gas bubbles. Determining mass flow in the vicinity of a pellet thus represents a parameter for quantifying the reaction efficiency and its dependence on time or external reaction conditions. Field gradient Nuclear Magnetic Resonance (NMR) methods are suggested as a tool for providing parameters sensitive to this mass flow in a contact-free and non-invasive way. For the example of bubble-forming hydrogen peroxide decomposition in an alumina pellet, the dependence of the mean-squared displacement of fluid molecules on spatial direction, observation time and reaction time is presented, and multi-pulse techniques are employed in order to separate molecular displacements from coherent and incoherent motion on the timescale of the experiment. The reaction progress is followed until the complete decomposition of H2O2. Copyright © 2011 Elsevier Inc. All rights reserved.

  17. Steady and nonsteady rates of reaction in a heterogeneously catalyzed reaction: Oxidation of CO on platinum, experiments and simulations (United States)

    Ehsasi, M.; Matloch, M.; Frank, O.; Block, J. H.; Christmann, K.; Rys, F. S.; Hirschwald, W.


    The rate of reaction for oxidation of CO over (210) and (111) single-crystal surfaces of platinum has been studied as a function of reactant pressures (PO2,PCO) and sample temperature (T), both experimentally and by computer simulation. Experimental results on both surfaces show regions with a steady high rate of reaction followed by a nonsteady transition region and, at high CO pressures, a region with low reactivity caused by CO poisoning of the surface. At constant sample temperature, the transition region can be narrow and depends critically on the ratio of the gas phase concentration of reactants (PCO/PO2). The temperature dependences of the experimental data indicate that the critical ratio and the details for the occurrence of CO poisoning are strongly affected by surface processes such as adsorption, desorption, and diffusion ordering and reconstruction phenomena. A computer simulation model of the Langmuir-Hinshelwood surface reaction as developed by Ziff et al. was used for the simulation of the reaction under flow conditions. The initial fair agreement between this model and the experiment can be significantly improved if processes such as adsorption, desorption, and diffusion are taken into account in an extended simulation model which in turn provides an insight into the kinetics of adsorbate poisoning and the effect of adsorbate-induced processes on the reaction.

  18. [2+2+2] Cycloaddition Reactions of Macrocyclic Systems Catalyzed by Transition Metals. A Review

    Directory of Open Access Journals (Sweden)

    Anna Roglans


    Full Text Available Polyalkyne and enediyne azamacrocycles are prepared from arenesulfonamides and various alkyne and alkene derivatives either under basic or neutral conditions. The new family of macrocyclic substrates is tested in the [2+2+2] cycloaddition reaction. Several catalysts are used for the cycloisomerization reaction, and their enantioinduction is evaluated as appropriate. The effect of the structural features of the macrocycles, namely the ring size, substituents in precise positions and the number and type of unsaturations, on the [2+2+2] cycloaddition reaction has also been studied.

  19. Influence of the reaction conditions on the enzyme catalyzed transesterification of castor oil

    DEFF Research Database (Denmark)

    Andrade, Thalles Allan; Errico, Massimiliano; Christensen, Knud Villy


    The identification of the influence of the reaction parameters is of paramount importance when defining a process design. In this work, non-edible castor oil was reacted with methanol to produce a possible component for biodiesel blends, using liquid enzymes as the catalyst. Temperature, alcohol......-to-oil molar ratio, enzyme and added water contents were the reaction parameters evaluated in the transesterification reactions. The optimal conditions, giving the optimal final FAME yield and FFA content in the methyl ester-phase was identified. At 35 °C, 6.0 methanol-to-oil molar ratio, 5 wt% of enzyme and 5...

  20. New method for exploring deactivation kinetics in copper-catalyzed atom-transfer-radical reactions. (United States)

    Zerk, Timothy J; Bernhardt, Paul V


    Copper polyamine complexes are among the most utilized catalysts for controlled radical polymerization reactions. Copper(I) complexes may react reversibly with an alkyl halide to form an alkyl radical, which promotes polymerization, and a copper(II) halido complex in a step known as activation. The kinetics of the reverse reaction between the alkyl radical and higher oxidation-state copper complex (deactivation) are less studied because these reactions approach diffusion-controlled rates, and it is difficult to isolate or quantify the concentration of the alkyl radical (R(•)) in situ. Herein we report a broadly applicable electrochemical technique for simultaneously measuring the kinetics of deactivation and kinetics of activation.

  1. Thiamine inhibits formation of dityrosine, a specific marker of oxidative injury, in reactions catalyzed by oxoferryl forms of hemoglobin. (United States)

    Stepuro, A I; Adamchuk, R I; Oparin, A Yu; Stepuro, I I


    Effects of thiamine and its derivatives on inhibition of dityrosine formation were studied in reactions catalyzed by oxoferryl forms of hemoglobin. At high thiamine concentrations, a complete inhibition of dityrosine formation was observed due to interaction of tyrosyl radicals with thiamine tricyclic and thiol forms. In neutral and alkaline media, tyrosyl radicals oxidized thiamine to thiochrome, oxodihydrothiochrome, and thiamine disulfide. In the absence of tyrosine, oxoferryl forms of hemoglobin manifested peroxidase activity towards thiamine and its phosphate esters by inducing their oxidation to disulfide compounds, thiochrome, oxodihydrothiochrome, and their phosphate esters, respectively, in neutral media. Thiamine and its phosphate esters were oxidized by both oxoferryl forms of hemoglobin, viz., +*Hb(IV=O) (compound I with an additional radical on the globin) and Hb(IV=O) (compound II). Putative mechanisms of thiamine conversions under oxidative stress and the protective role of hydrophobic thiamine metabolites are discussed.

  2. Sodium ascorbate kills Candida albicans in vitro via iron-catalyzed Fenton reaction: importance of oxygenation and metabolism. (United States)

    Avci, Pinar; Freire, Fernanda; Banvolgyi, Andras; Mylonakis, Eleftherios; Wikonkal, Norbert M; Hamblin, Michael R


    Ascorbate can inhibit growth and even decrease viability of various microbial species including Candida albicans. However the optimum conditions and the mechanism of action are unclear. Materials/methodology: Candida albicans shaken for 90 min in a buffered solution of ascorbate (90 mM) gave a 5-log reduction of cell viability, while there was no killing without shaking, in growth media with different carbon sources or at 4°C. Killing was inhibited by the iron chelator 2,2'-bipyridyl. Hydroxyphenyl fluorescein probe showed the intracellular generation of hydroxyl radicals. Ascorbate-mediated killing of C. albicans depends on oxygenation and metabolism, involves iron-catalyzed generation of hydroxyl radicals via Fenton reaction and depletion of intracellular NADH. Ascorbate could serve as a component of a topical antifungal therapy.

  3. Transition metal catalyzed carbonylation reactions carbonylative activation of C-X bonds

    CERN Document Server

    Beller, Matthias


    This book provides students and researchers in organic synthesis with a detailed discussion of carbonylation from the basics through to applications. It discusses the past, present and future of carbonylation reactions.

  4. DNA-catalyzed Henry reaction in pure water and the striking influence of organic buffer systems. (United States)

    Häring, Marleen; Pérez-Madrigal, Maria M; Kühbeck, Dennis; Pettignano, Asja; Quignard, Françoise; Díaz, David Díaz


    In this manuscript we report a critical evaluation of the ability of natural DNA to mediate the nitroaldol (Henry) reaction at physiological temperature in pure water. Under these conditions, no background reaction took place (i.e., control experiment without DNA). Both heteroaromatic aldehydes (e.g., 2-pyridinecarboxaldehyde) and aromatic aldehydes bearing strong or moderate electron-withdrawing groups reacted satisfactorily with nitromethane obeying first order kinetics and affording the corresponding β-nitroalcohols in good yields within 24 h. In contrast, aliphatic aldehydes and aromatic aldehydes having electron-donating groups either did not react or were poorly converted. Moreover, we discovered that a number of metal-free organic buffers efficiently promote the Henry reaction when they were used as reaction media without adding external catalysts. This constitutes an important observation because the influence of organic buffers in chemical processes has been traditionally underestimated.

  5. DNA-Catalyzed Henry Reaction in Pure Water and the Striking Influence of Organic Buffer Systems

    Directory of Open Access Journals (Sweden)

    Marleen Häring


    Full Text Available In this manuscript we report a critical evaluation of the ability of natural DNA to mediate the nitroaldol (Henry reaction at physiological temperature in pure water. Under these conditions, no background reaction took place (i.e., control experiment without DNA. Both heteroaromatic aldehydes (e.g., 2-pyridinecarboxaldehyde and aromatic aldehydes bearing strong or moderate electron-withdrawing groups reacted satisfactorily with nitromethane obeying first order kinetics and affording the corresponding β-nitroalcohols in good yields within 24 h. In contrast, aliphatic aldehydes and aromatic aldehydes having electron-donating groups either did not react or were poorly converted. Moreover, we discovered that a number of metal-free organic buffers efficiently promote the Henry reaction when they were used as reaction media without adding external catalysts. This constitutes an important observation because the influence of organic buffers in chemical processes has been traditionally underestimated.

  6. Efficient buchwald hartwig reaction catalyzed by spions-bis(NHC-Pd(II

    Directory of Open Access Journals (Sweden)

    Marzieh Ghotbinejad


    Full Text Available A powerful and convenient reaction procedure for the C-N coupling reaction (the Buchwald-Hartwig reaction, yielding products of N-arylanilines and N-arylamines in both conventional heating and microwave irradiation has been reported. The protocol utilizes a stable and new supper ferromagnetic nanoparticle chelating N-heterocyclic dicarbene palladium(II complex (Pd-NHC as catalyst which helps/allows us to complete the reaction with only 0.002 mol% Pd producing high yield products. We also examined the reusability of the catalyst. It was found that the catalyst could be recovered by external magnetic field and  reused for seven times without obvious loss in catalytic activity.

  7. Pd-NHC catalyzed conjugate addition versus the Mizoroki-Heck reaction. (United States)

    Gottumukkala, Aditya L; de Vries, Johannes G; Minnaard, Adriaan J


    Ace of base: A catalytic system is presented that, solely by choice of the base, selectively switches between conjugate addition and the Mizoroki-Heck reaction of aryl halides with Michael acceptors (see scheme; R, R' = alkyl, aryl). For conjugate addition reactions, this avoids the preparation and use of organometallics. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Recent progress in transition-metal-catalyzed reduction of molecular dinitrogen under ambient reaction conditions. (United States)

    Nishibayashi, Yoshiaki


    This paper describes our recent progress in catalytic nitrogen fixation by using transition-metal-dinitrogen complexes as catalysts. Two reaction systems for the catalytic transformation of molecular dinitrogen into ammonia and its equivalent such as silylamine under ambient reaction conditions have been achieved by the molybdenum-, iron-, and cobalt-dinitrogen complexes as catalysts. Many new findings presented here may provide new access to the development of economical nitrogen fixation in place of the Haber-Bosch process.

  9. Pd(II/HPMoV-Catalyzed Direct Oxidative Coupling Reaction of Benzenes with Olefins

    Directory of Open Access Journals (Sweden)

    Yasutaka Ishii


    Full Text Available The direct aerobic coupling reaction of arenes with olefins was successfully achieved by the use of Pd(OAc2/molybdovanadophosphoric acid (HPMoV as a key catalyst under 1 atm of dioxygen. This catalytic system could be extended to the coupling reaction of various substituted benzenes with olefins such as acrylates, aclrolein, and ethylene through the direct aromatic C-H bond activation.

  10. Low-temperature superacid catalysis: Reactions of n - butane and propane catalyzed by iron- and manganese-promoted sulfated zirconia

    Energy Technology Data Exchange (ETDEWEB)

    Tsz-Keung, Cheung; d`Itri, J.L.; Lange, F.C.; Gates, B.C. [Univ. of California, Davis, CA (United States)


    The primary goal of this project is to evaluate the potential value of solid superacid catalysts of the sulfated zirconia type for light hydrocarbon conversion. The key experiments catalytic testing of the performance of such catalysts in a flow reactor fed with streams containing, for example, n-butane or propane. Fe- and Mn-promoted sulfated zirconia was used to catalyze the conversion of n-butane at atmospheric pressure, 225-450{degrees}C, and n-butane partial pressures in the range of 0.0025-0.01 atm. At temperatures <225{degrees}C, these reactions were accompanied by cracking; at temperatures >350{degrees}C, cracking and isomerization occurred. Catalyst deactivation, resulting at least in part from coke formation, was rapid. The primary cracking products were methane, ethane, ethylene, and propylene. The observation of these products along with an ethane/ethylene molar ratio of nearly 1 at 450{degrees}C is consistent with cracking occurring, at least in part, by the Haag-Dessau mechanism, whereby the strongly acidic catalyst protonates n-butane to give carbonium ions. The rate of methane formation from n-butane cracking catalyzed by Fe- and Mn-promoted sulfated zirconia at 450{degrees}C was about 3 x 10{sup -8} mol/(g of catalyst {center_dot}s). The observation of butanes, pentanes, and methane as products is consistent with Olah superacid chemistry, whereby propane is first protonated by a very strong acid to form a carbonium ion. The carbonium ion then decomposes into methane and an ethyl cation which undergoes oligocondensation reactions with propane to form higher molecular weight alkanes. The results are consistent with the identification of iron- and manganese-promoted sulfated zirconia as a superacid.

  11. Theoretical insights into the sites and mechanisms for base catalyzed esterification and aldol condensation reactions over Cu. (United States)

    Neurock, Matthew; Tao, Zhiyuan; Chemburkar, Ashwin; Hibbitts, David D; Iglesia, Enrique


    Condensation and esterification are important catalytic routes in the conversion of polyols and oxygenates derived from biomass to fuels and chemical intermediates. Previous experimental studies show that alkanal, alkanol and hydrogen mixtures equilibrate over Cu/SiO 2 and form surface alkoxides and alkanals that subsequently promote condensation and esterification reactions. First-principle density functional theory (DFT) calculations were carried out herein to elucidate the elementary paths and the corresponding energetics for the interconversion of propanal + H 2 to propanol and the subsequent C-C and C-O bond formation paths involved in aldol condensation and esterification of these mixtures over model Cu surfaces. Propanal and hydrogen readily equilibrate with propanol via C-H and O-H addition steps to form surface propoxide intermediates and equilibrated propanal/propanol mixtures. Surface propoxides readily form via low energy paths involving a hydrogen addition to the electrophilic carbon center of the carbonyl of propanal or via a proton transfer from an adsorbed propanol to a vicinal propanal. The resulting propoxide withdraws electron density from the surface and behaves as a base catalyzing the activation of propanal and subsequent esterification and condensation reactions. These basic propoxides can readily abstract the acidic C α -H of propanal to produce the CH 3 CH (-) CH 2 O* enolate, thus initiating aldol condensation. The enolate can subsequently react with a second adsorbed propanal to form a C-C bond and a β-alkoxide alkanal intermediate. The β-alkoxide alkanal can subsequently undergo facile hydride transfer to form the 2-formyl-3-pentanone intermediate that decarbonylates to give the 3-pentanone product. Cu is unique in that it rapidly catalyzes the decarbonylation of the C 2n intermediates to form C 2n-1 3-pentanone as the major product with very small yields of C 2n products. This is likely due to the absence of Brønsted acid sites

  12. Degradation of Anthraquinone Dye Reactive Blue 4 in Pyrite Ash Catalyzed Fenton Reaction

    Directory of Open Access Journals (Sweden)

    Milena Becelic-Tomin


    Full Text Available Pyrite ash (PA is created by burning pyrite in the chemical production of sulphuric acid. The high concentration of iron oxide, mostly hematite, present in pyrite ash, gives the basis for its application as a source of catalytic iron in a modified Fenton process for anthraquinone dye reactive blue 4 (RB4 degradation. The effect of various operating variables such as catalyst and oxidant concentration, initial pH and RB4 concentration on the abatement of total organic carbon, and dye has been assessed in this study. Here we show that degradation of RB4 in the modified Fenton reaction was efficient under the following conditions: pH=2.5; [PA]0=0.2 g L−1; [H2O2]0=5 mM and initial RB4 concentration up to 100 mg L−1. The pyrite ash Fenton reaction can overcome limitations observed from the classic Fenton reaction, such as the early termination of the Fenton reaction. Metal (Pb, Zn, and Cu content of the solution after the process suggests that an additional treatment step is necessary to remove the remaining metals from the water. These results provide basic knowledge to better understand the modified, heterogeneous Fenton process and apply the PA Fenton reaction for the treatment of wastewaters which contains anthraquinone dyes.

  13. Regioselectivity and Reaction Mechanism of Ru-Catalyzed Hydrogenolysis of Squalane and Model Alkanes. (United States)

    Nakagawa, Yoshinao; Oya, Shin-Ichi; Kanno, Daisuke; Nakaji, Yosuke; Tamura, Masazumi; Tomishige, Keiichi


    The dependence of the C-C hydrogenolysis activity on reaction parameters and the structure of the substrate alkanes was investigated for Ru/CeO2 catalyst with very small (dispersion: H/Ru=0.89) Ru particles. The substrate concentration and reaction temperature did not have a significant effect on the selectivity pattern, except that methane production was promoted at high temperatures. However, the hydrogen pressure had a marked effect on the selectivity pattern. Ctertiary -C bond dissociation, terminal Csecondary -Cprimary bond dissociation, and fragmentation to form excess methane had negative reaction order with respect to hydrogen partial pressure, whereas Csecondary -Csecondary bond dissociation had an approximately zero reaction order. Therefore, a high hydrogen pressure is essential for the regioselective hydrogenolysis of Csecondary -Csecondary bonds in squalane. Ru/SiO2 catalyst with larger Ru particles showed similar changes in the product distribution during the change in hydrogen pressure. The reaction mechanism for each type of C-C bond dissociation is proposed based on reactivity trends and DFT calculations. The proposed intermediate species for the internal Csecondary -Csecondary dissociation, terminal Csecondary -Cprimary dissociation, and Ctertiary -C dissociation is alkyls, alkylidynes, and alkenes, respectively. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Imidazole-based Vanadium Complexes as Haloperoxidase Models ...

    African Journals Online (AJOL)


    Ryan S. Walmsley* and Zenixole R. Tshentu. Department ... The heterogeneous catalysts also proved to be recyclable for this reaction, with no appreciable loss in activity even after three catalytic ..... Figure 3 Spectrophotometric titration of 2a (1 × 10–4 mM) with one-drop portions of H2O2 (5 × 10–2 mM) in water. The inset ...

  15. Chemoselective Boron-Catalyzed Nucleophilic Activation of Carboxylic Acids for Mannich-Type Reactions. (United States)

    Morita, Yuya; Yamamoto, Tomohiro; Nagai, Hideoki; Shimizu, Yohei; Kanai, Motomu


    The carboxyl group (COOH) is an omnipresent functional group in organic molecules, and its direct catalytic activation represents an attractive synthetic method. Herein, we describe the first example of a direct catalytic nucleophilic activation of carboxylic acids with BH3·SMe2, after which the acids are able to act as carbon nucleophiles, i.e. enolates, in Mannich-type reactions. This reaction proceeds with a mild organic base (DBU) and exhibits high levels of functional group tolerance. The boron catalyst is highly chemoselective toward the COOH group, even in the presence of other carbonyl moieties, such as amides, esters, or ketones. Furthermore, this catalytic method can be extended to highly enantioselective Mannich-type reactions by using a (R)-3,3'-I2-BINOL-substituted boron catalyst.

  16. Palladium-Catalyzed Reactions of Arylindium Reagents Prepared Directly from Aryl Iodides and Indium Metal (United States)

    Papoian, Vardan


    Treatment of aryl iodides with indium metal in the presence of lithium chloride leads to the formation of an organoindium reagent capable of participating in cross-coupling reactions under transition-metal catalysis. Combination with aryl halides in the presence of 5 mol% Cl2Pd(dppf) furnishes biaryl compounds in good yields; similarly, reaction with acyl halides or allylic acetates/carbonates in the presence of 5–10 mol % palladium catalyst leads to arylketones and allylic substitution products, respectively, in moderate yields. The reactions are tolerant of the presence of protic solvents, and ~85% of the indium metal employed can be recovered by reduction of the residual indium salts with zinc(0). PMID:18722408

  17. Pd-catalyzed Heck reactions of aryl bromides with 1,2-diarylethenes

    Energy Technology Data Exchange (ETDEWEB)

    Limberger, Jones; Poersch, Silvia; Monteiro, Adriano L., E-mail: adriano.monteiro@ufrgs.b [Universidade Federal do Rio Grande do Sul (LCM/UFRGS), Porto Alegre, RS (Brazil). Lab. of Molecular Catalysis


    A catalytic system composed of Pd(OAc){sub 2} and P(o-tol){sub 3} was found to be effective for the Heck reaction of aryl bromides with diarylethylenes. Using K{sub 2}CO{sub 3} as a base and DMF as a solvent, trisubstituted olefins were obtained in good to excellent yields. Aryl bromides containing an electron-withdrawing group in para position were less reactive for the Heck coupling reaction and gave substantial amount of homocoupling by-product suggesting that oxidative addition is not the rate-determining step. Electron withdrawing group substituent in the para position of stilbene affects the regioselectivity of the reaction. In this case, the phenyl group from the Ph-Pd complex migrates preferentially to the same carbon of the double bond to which the phenyl is bonded. Finally, a one pot sequential double Heck arylation of styrene was performed, giving trisubstituted olefin with an overall yield of 73%. (author)

  18. Heterogeneous Photo-Fenton Reaction Catalyzed by Nanosized Iron Oxides for Water Treatment

    Directory of Open Access Journals (Sweden)

    Chuan Wang


    Full Text Available Great efforts have been exerted in overcoming the drawbacks of the Fenton reaction for water treatment applications. The drawbacks include pH confinement, handling of iron sludge, slow regeneration of Fe(II, and so forth. This paper highlights the recent developments in the heterogeneous photo-Fenton reaction which utilizes nanosized iron oxides as catalyst for maximizing the activity due to the enhanced physical or chemical properties brought about by the unique structures. This paper also summarizes the fundamentals of the Fenton reaction, which determine the inherent drawbacks and associated advances, to address the advantages of iron oxides and nanosized iron oxides. Tips for applying this method in water treatment are also provided. Given that the environmental effect of nanosized iron oxides is not yet well established, rapid research growth may occur in the near future to advance this promising technology toward water treatment once it is smartly coupled with conventional technologies.

  19. Kinetics based reaction optimization of enzyme catalyzed reduction of formaldehyde to methanol with synchronous cofactor regeneration. (United States)

    Marpani, Fauziah; Sárossy, Zsuzsa; Pinelo, Manuel; Meyer, Anne S


    Enzymatic reduction of carbon dioxide (CO2 ) to methanol (CH3 OH) can be accomplished using a designed set-up of three oxidoreductases utilizing reduced pyridine nucleotide (NADH) as cofactor for the reducing equivalents electron supply. For this enzyme system to function efficiently a balanced regeneration of the reducing equivalents during reaction is required. Herein, we report the optimization of the enzymatic conversion of formaldehyde (CHOH) to CH3 OH by alcohol dehydrogenase, the final step of the enzymatic redox reaction of CO2 to CH3 OH, with kinetically synchronous enzymatic cofactor regeneration using either glucose dehydrogenase (System I) or xylose dehydrogenase (System II). A mathematical model of the enzyme kinetics was employed to identify the best reaction set-up for attaining optimal cofactor recycling rate and enzyme utilization efficiency. Targeted process optimization experiments were conducted to verify the kinetically modeled results. Repetitive reaction cycles were shown to enhance the yield of CH3 OH, increase the total turnover number (TTN) and the biocatalytic productivity rate (BPR) value for both system I and II whilst minimizing the exposure of the enzymes to high concentrations of CHOH. System II was found to be superior to System I with a yield of 8 mM CH3 OH, a TTN of 160 and BPR of 24 μmol CH3 OH/U · h during 6 hr of reaction. The study demonstrates that an optimal reaction set-up could be designed from rational kinetics modeling to maximize the yield of CH3 OH, whilst simultaneously optimizing cofactor recycling and enzyme utilization efficiency. © 2017 Wiley Periodicals, Inc.

  20. Metal-catalyzed Asymmetric Hetero-Diels-Alder Reactions of Unactivated Dienes with Glyoxylates

    DEFF Research Database (Denmark)

    Johannsen, Mogens; Yao, Sulan; Graven, Anette


    The development of a catalytic asymmetric hetero-Diels-Alder methodology for the reaction of unactivated dienes with glyoxylates is presented. Several different asymmetric catalysts can be used, but copper-bisoxazolines and aluminium-BINOL give the highest yield, and the best chemo- and enantiose......The development of a catalytic asymmetric hetero-Diels-Alder methodology for the reaction of unactivated dienes with glyoxylates is presented. Several different asymmetric catalysts can be used, but copper-bisoxazolines and aluminium-BINOL give the highest yield, and the best chemo...

  1. Palladium-catalyzed cross coupling reactions of 4-bromo-6H-1,2-oxazines

    Directory of Open Access Journals (Sweden)

    Reinhold Zimmer


    Full Text Available A number of 4-aryl- and 4-alkynyl-substituted 6H-1,2-oxazines 8 and 9 have been prepared in good yields via cross coupling reactions of halogenated precursors 2, which in turn are easily accessible by bromination of 6H-1,2-oxazines 1. Lewis-acid promoted reaction of 1,2-oxazine 9c with 1-hexyne provided alkynyl-substituted pyridine derivative 12 thus demonstrating the potential of this approach for the synthesis of pyridines.


    In the presence of a catalytic amount of RuCl2(PPh3)3, a cross-coupling of 3-buten-2-ol with aldehydes and imines was developed via a tandem olefin migration--aldol--Mannich reaction in bmim[PF6]. With In(OAc)3 as a co-catalyst, a-vinylbenzyl alcohol and aldehydes underwent sim...

  3. Ion sensitivity of the light reaction catalyzed by enzyme preparations from Photobacterium phosphoreum

    NARCIS (Netherlands)

    Terpstra, Willemke; Eijk, H.G. van


    Cations, especially divalent ones, increase the intensity of the light flash, obtained by adding FMNH to luciferase preparations containing palmital. Besides, they cause a more rapid decay of the light reaction. Probably, the effect is due to inhibition of the oxidation of FMNH independent of the

  4. The Effect of Temperature on the Enzyme-Catalyzed Reaction: Insights from Thermodynamics (United States)

    Aledo, Juan Carlos; Jimenez-Riveres, Susana; Tena, Manuel


    When teaching the effect of temperature on biochemical reactions, the problem is usually oversimplified by confining the thermal effect to the catalytic constant, which is identified with the rate constant of the elementary limiting step. Therefore, only positive values for activation energies and values greater than 1 for temperature coefficients…

  5. Hydrogen- Bond- Assisted Activation of Allylic Alcohols for Palladium- Catalyzed Coupling Reactions

    NARCIS (Netherlands)

    Gumrukcu, Y.; de Bruin, B.; Reek, J.


    We report direct activation of allylic alcohols using a hydrogen-bond-assisted palladium catalyst and use this for alkylation and amination reactions. The novel catalyst comprises a palladium complex based on a functionalized monodentate phosphoramidite ligand in combination with urea additives and

  6. C (sp2)–C (sp2) cross coupling reaction catalyzed by a palladacycle ...

    Indian Academy of Sciences (India)

    =C(O)(C10H7)] PdCl2} as efficient catalyst has been investigated. The mononuclear palladacycle complex showed excellent activity in aqueous phase including the C(sp2)–C(sp2) cross coupling reactions. The advantages of the protocol are ...

  7. Cross-coupling reaction of alkyl halides with grignard reagents catalyzed by Ni, Pd, or Cu complexes with pi-carbon ligand(s). (United States)

    Terao, Jun; Kambe, Nobuaki


    Transition metal-catalyzed cross-coupling reactions of organic halides and pseudo-halides containing a C-X bond (X = I, Br, Cl, OTf, OTs, etc.) with organometallic reagents are among the most important transformations for carbon-carbon bond formation between a variety of sp, sp(2), and sp(3)-hybridized carbon atoms. In particular, researchers have widely employed Ni- and Pd-catalyzed cross-coupling to synthesize complex organic structures from readily available components. The catalytic cycle of this process comprises oxidative addition, transmetalation, and reductive elimination steps. In these reactions, various organometallic reagents could bear a variety of R groups (alkyl, vinyl, aryl, or allyl), but the coupling partner has been primarily limited to sp and sp(2) carbon compounds: alkynes, alkenes, and arenes. With alkyl coupling partners, these reactions typically run into two problems within the catalytic cycle. First, oxidative addition of alkyl halides to a metal catalyst is generally less efficient than that of aryl or alkenyl compounds. Second, the alkylmetal intermediates formed tend to undergo intramolecular beta-hydrogen elimination. In this Account, we describe our efforts to overcome these problems for Ni and Pd chemistry. We have developed new catalytic systems that do not involve M(0) species but proceed via an anionic complex as the key intermediate. For example, we developed a unique cross-coupling reaction of alkyl halides with organomagnesium or organozinc reagents catalyzed by using a 1,3-butadiene as the additive. This reaction follows a new catalytic pathway: the Ni or Pd catalyst reacts first with R-MgX to form an anionic complex, which then reacts with alkyl halides. Bis-dienes were also effective additives for the Ni-catalyzed cross-coupling reaction of organozinc reagents with alkyl halides. This catalytic system tolerates a wide variety of functional groups, including nitriles, ketones, amides, and esters. In addition, we have extended

  8. Ferric chloride-catalyzed reaction of [60]fullerene with tert-butyl N-substituted carbamates: synthesis of oxazolidino[4,5:1,2][60]fullerenes. (United States)

    You, Xun; Wang, Guan-Wu


    The rare oxazolidinofullerenes have been prepared by the ferric chloride-catalyzed reaction of [60]fullerene with various tert-butyl N-substituted carbamates via t-Bu-O bond cleavage and heteroannulation under mild conditions. A possible mechanism for the formation of oxazolidinofullerenes is proposed.

  9. Structure–activity relationships of oligocationic, ammonium-functionalized triarylphosphines as ligands in the Pd-Catalyzed Suzuki–Miyaura reaction

    NARCIS (Netherlands)

    Snelders, D.J.M.; van der Burg, C.; Lutz, M.; Spek, A.L.; van Koten, G.; Klein Gebbink, R.J.M.


    A series of oligocationic triarylphosphine ligands, containing a varying number (from 2 to 6) of meta-ammoniomethyl substituents, have been synthesized, characterized, and tested as ligands in the Pd-catalyzed Suzuki–Miyaura cross-coupling reaction. By systematic catalytic investigations and

  10. Uptake kinetics and biodistribution of C-14-D-luciferin-a radiolabeled substrate for the firefly luciferase catalyzed bioluminescence reaction : impact on bioluminescence based reporter gene imaging

    NARCIS (Netherlands)

    Berger, Frank; Paulmurugan, Ramasamy; Bhaumik, Srabani; Gambhir, Sanjiv Sam


    Purpose Firefly luciferase catalyzes the oxidative decarboxylation of D-luciferin to oxyluciferin in the presence of cofactors, producing bioluminescence. This reaction is used in optical bioluminescence-based molecular imaging approaches to detect the expression of the firefly luciferase reporter

  11. Copper-Catalyzed Denitrogenative Transannulation Reaction of Pyridotriazoles: Synthesis of Imidazo[1,5-a]pyridines with Amines and Amino Acids. (United States)

    Joshi, Abhisek; Mohan, Darapaneni Chandra; Adimurthy, Subbarayappa


    The copper-catalyzed aerobic oxidative synthesis of imidazo[1,5-a]pyridines via cascade denitrogenative transannulation reaction of pyridotriazoles with benzylamines with good functional group tolerance is developed. The present methodology is also applicable to amino acids to obtain imidazo[1,5-a]pyridines via decarboxylative oxidative cyclization.

  12. "N"-Heterocyclic Carbene-Catalyzed Reaction of Chalcone and Cinnamaldehyde to Give 1,3,4-Triphenylcyclopentene Using Organocatalysis to Form a Homoenolate Equivalent (United States)

    Snider, Barry B.


    In this experiment, students carry out a modern organocatalytic reaction using IMes·HCl and NaOH to catalyze the formation of 1,3,4-triphenylcyclopentene from cinnamaldehyde and chalcone in water. Deprotonation of IMes·HCl with NaOH forms the "N"-heterocyclic carbene IMes that reacts with cinnamaldehyde to form a homoenolate equivalent…

  13. Process limitations of a whole-cell P450 catalyzed reaction using a CYP153A-CPR fusion construct expressed in Escherichia coli

    DEFF Research Database (Denmark)

    Lundemo, M. T.; Notonier, S.; Striedner, G.


    fatty acids at the terminal position. ω-Hydroxylated fatty acids can be used in the field of high-end polymers and in the cosmetic and fragrance industry. Here, we have identified the limitations for implementation of a whole-cell P450-catalyzed reaction by characterizing the chosen biocatalyst as well...

  14. High Pressure Diels Alder Reactions of 1-Vinyl-2,2,6-trimethylcyclohexene Catalyzed by Chiral Lewis Acids; An Enantioselective Route to a Drimane Sesquiterpene Precursor.

    NARCIS (Netherlands)

    Knol, Joop; Meetsma, Auke; Feringa, Bernard


    The Diels Alder reaction of 1-vinyl-2,2,6-trimethylcyclohexene and 3-((E)-3-(methoxycarbonyl)propenoyl)-1,3-oxazolidin-2-one under high pressure, catalyzed by a chiral bis-imine copper(II) complex, yields a drimane sesquiterpene precursor in a highly regio- and diastereoselective manner with

  15. Highly enantioselective Friedel-Crafts alkylation reaction catalyzed by rosin-derived tertiary amine-thiourea: synthesis of modified chromanes with anticancer potency. (United States)

    Jiang, Xianxing; Wu, Lipeng; Xing, Yanhong; Wang, Long; Wang, Shoulei; Chen, Zongyao; Wang, Rui


    We present herein for the first time the synthesis and preliminary biological evaluation of various modified chromanes via a rosin-derived tertiary amine-thiourea-catalyzed highly enantioselective Friedel-Crafts alkylation reaction. This journal is © The Royal Society of Chemistry 2012

  16. Phospholipase D (PLD) catalyzed synthesis of phosphatidyl-glucose in biphasic reaction system. (United States)

    Song, Shuang; Cheong, Ling-Zhi; Guo, Zheng; Kristensen, Kasper; Glasius, Marianne; Jensen, Henrik Max; Bertelsen, Kresten; Tan, Tianwei; Xu, Xuebing


    Presence of saccharides in glycophospholipids may increase its potential to form supramolecular structures, which are not only stable for an extended period of time as compared to other PLs like phosphatidylcholine, but may also confer an antioxidative property. Most syntheses routes for glycophospholipid involved the usage of toxic chemicals or solvents, complicated steps and low yield. The present work attempted to develop an enzymatic method for the production of glycophospholipids. Phosphatidyl-glucose (PL-Glu) was synthesized as a model glycophospholipid. The effects of organic solvents, water content, substrate ratio, pH and temperature on glycophospholipid yield (mol%) were examined in this study. Under optimum reaction conditions, more than 95 mol% of PL-Glu was obtained in 1.5 h. The conversion rate is significantly higher than previously reported findings. The established model reaction system in the present work was used to synthesize other types of glycophospholipid. Copyright © 2012 Elsevier Ltd. All rights reserved.

  17. Coupling Reactions of Carbon Dioxide with Epoxides Catalyzed by Vanadium Aminophenolate Complexes. (United States)

    Elkurtehi, Ali I; Kerton, Francesca M


    A series of vanadium compounds supported by tetradentate aminobis(phenolate) ligands were screened for catalytic reactivity in the reaction of propylene oxide (PO) with CO2 : [VO(OMe)(O2 NOBuMeMeth )], [VO(OMe)(ON2 OBuMe )], [VO(OMe)(O2 NNBuBuPy )], and [VO(OMe)(O2 NOBuBuFurf )]. They showed similar reactivities, but reaction rates were higher for [VO(OMe)(ON2 OBuMe )], which was studied in more detail. Turnover frequencies for conversion of PO over 500 h-1 were observed. Activation energies were determined experimentally through in situ IR spectroscopy for propylene carbonate (48.2 kJ mol-1 ), styrene carbonate (45.6 kJ mol-1 ), and cyclohexene carbonate (54.7 kJ mol-1 ) formation. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Synthesis of L-Ascorbyl Flurbiprofenate by Lipase-Catalyzed Esterification and Transesterification Reactions


    Xin, Jia-ying; Sun, Li-rui; Chen, Shu-ming; Wang, Yan; Xia, Chun-gu


    The synthesis of L-ascorbyl flurbiprofenate was achieved by esterification and transesterification in nonaqueous organic medium with Novozym 435 lipase as biocatalyst. The conversion was greatly influenced by the kinds of organic solvents, speed of agitation, catalyst loading amount, reaction time, and molar ratio of acyl donor to L-ascorbic acid. A series of solvents were investigated, and tert-butanol was found to be the most suitable from the standpoint of the substrate solubility and the ...

  19. Laboratory Studies of Hydrogen Gas Generation Using the Cobalt Chloride Catalyzed Sodium Borohydride-Water Reaction (United States)


    reaction to generate hydrogen gas to inflate lighter-than-air vehicles . RESULTS When using CoCl2 as a catalyst, we discovered that distilled or...driving prices up. Consequently, the use of hydrogen gas to inflate LTA vehicles is gaining greater acceptance; many countries (military and commercial...due to leakage, safety, and size concerns. Hydrogen is less flammable than gasoline. In summary, the demand to use LTA vehicles for military and

  20. Factors influencing the mechanism of surfactant catalyzed reaction of vitamin C-ferric chloride hexahydrate system (United States)

    Farrukh, Muhammad Akhyar; Kauser, Robina; Adnan, Rohana


    The kinetics of vitamin C by ferric chloride hexahydrate has been investigated in the aqueous ethanol solution of basic surfactant viz. octadecylamine (ODA) under pseudo-first order conditions. The critical micelle concentration (CMC) of surfactant was determined by surface tension measurement. The effect of pH (2.5-4.5) and temperature (15-35°C) in the presence and absence of surfactant were investigated. Activation parameters, Δ E a, Δ H #, Δ S #, Δ G ≠, for the reaction were calculated by using Arrhenius and Eyring plot. Surface excess concentration (Γmax), minimum area per surfactant molecule ( A min), average area occupied by each molecule of surfactant ( a), surface pressure at the CMC (Πmax), Gibb's energy of micellization (Δ G M°), Gibb's energy of adsorption (Δ G ad°), were calculated. It was found that the reaction in the presence of surfactant showed faster oxidation rate than the aqueous ethanol solution. Reaction mechanism has been deduced in the presence and absence of surfactant.

  1. Enzymatic Synthesis and Structural Characterization of Theanderose through Transfructosylation Reaction Catalyzed by Levansucrase from Bacillus subtilis CECT 39. (United States)

    Ruiz-Aceituno, Laura; Sanz, Maria Luz; de Las Rivas, Blanca; Muñoz, Rosario; Kolida, Sofia; Jimeno, Maria Luisa; Moreno, F Javier


    This work addresses the high-yield and fast enzymatic production of theanderose, a naturally occurring carbohydrate, also known as isomaltosucrose, whose chemical structure determined by NMR is α-d-glucopyranosyl-(1 → 6)-α-d-glucopyranosyl-(1 → 2)-β-d-fructofuranose. The ability of isomaltose to act as an acceptor in the Bacillus subtilis CECT 39 levansucrase-catalyzed transfructosylation reaction to efficiently produce theanderose in the presence of sucrose as a donor is described by using four different sucrose:isomaltose concentration ratios. The maximum theanderose concentration ranged from 122.4 to 130.4 g L -1 , was obtained after only 1 h and at a moderate temperature (37 °C), leading to high productivity (109.7-130.4 g L -1 h -1 ) and yield (up to 37.3%) values. The enzymatic synthesis was highly regiospecific, since no other detectable acceptor reaction products were formed. The development of efficient and cost-effective procedures for the biosynthesis of unexplored but appealing oligosaccharides as potential sweeteners, such as theanderose, could help to expand its potential applications which are currently limited by their low availability.

  2. Palladium(II)-Catalyzed C-H Bond Activation/C-C and C-O Bond Formation Reaction Cascade: Direct Synthesis of Coumestans. (United States)

    Neog, Kashmiri; Borah, Ashwini; Gogoi, Pranjal


    A palladium catalyzed cascade reaction of 4-hydroxycoumarins and in situ generated arynes has been developed for the direct synthesis of coumestans. This cascade strategy proceeds via C-H bond activation/C-O and C-C bond formations in a single reaction vessel. This methodology affords moderate to good yields of coumestans and is tolerant of a variety of functional groups including halide. The methodology was applied to the synthesis of natural product flemichapparin C.

  3. Cu/Pd-Catalyzed, Three-Component Click Reaction of Azide, Alkyne, and Aryl Halide: One-Pot Strategy toward Trisubstituted Triazoles. (United States)

    Wei, Fang; Li, Haoyu; Song, Chuanling; Ma, Yudao; Zhou, Ling; Tung, Chen-Ho; Xu, Zhenghu


    A Cu/Pd-catalyzed, three-component click reaction of azide, alkyne, and aryl halide has been developed. By using this Cu/Pd transmetalation relay catalysis, a variety of 1,4,5-trisubstituted 1,2,3-triazoles were quickly assembled in one step in high yields with complete regioselectivity, just like assembling Lego bricks. Notably, different from the well-established CuAAC click reactions only working on terminal alkynes, this reaction offers an alternative solution for the problem of the click reaction of internal alkynes.

  4. [Ligand intermediates in metal-catalyzed reactions]. Progress report, July 1, 1989--June 30, 1992

    Energy Technology Data Exchange (ETDEWEB)


    This report consists of sections on sigma bond complexes of alkenes, a new carbon-hydrogen bond activation reaction of alkene complexes, carbon-hydrogen bond migrations in alkylidene complexes, carbon- hydrogen bond migrations in alkyne complexes, synthesis, structure and reactivity of C{sub x} complexes, synthesis and reactivity of alcohol and ether complexes, new catalysts for the epimerization of secondary alcohols; carbon-hydrogen bond activation in alkoxide complexes, pi/sigma equilibria in metal/O=CXX` complexes, and other hydrocarbon ligands; miscellaneous.(WET)

  5. Linear polystyrene-stabilized PdO nanoparticle-catalyzed Mizoroki-Heck reactions in water. (United States)

    Ohtaka, Atsushi; Yamaguchi, Tomohiro; Teratani, Takuto; Shimomura, Osamu; Nomura, Ryôki


    Linear polystyrene-stabilized PdO nanoparticles (PS-PdONPs) were prepared by thermal decomposition of Pd(OAc)(2) in the presence of polystyrene. X-ray diffraction (XRD) and transmission electron microscopy (TEM) indicated the production of PdO nanoparticles. The loading of palladium was determined by inductively coupled plasma-atomic emission spectroscopy (ICP-AES). PS-PdONPs exhibited high catalytic activity for Mizoroki-Heck reactions under air in water and could be recycled without loss of activity.

  6. Linear Polystyrene-Stabilized PdO Nanoparticle-Catalyzed Mizoroki-Heck Reactions in Water

    Directory of Open Access Journals (Sweden)

    Takuto Teratani


    Full Text Available Linear polystyrene-stabilized PdO nanoparticles (PS-PdONPs were prepared by thermal decomposition of Pd(OAc2 in the presence of polystyrene. X-ray diffraction (XRD and transmission electron microscopy (TEM indicated the production of PdO nanoparticles. The loading of palladium was determined by inductively coupled plasma-atomic emission spectroscopy (ICP-AES. PS-PdONPs exhibited high catalytic activity for Mizoroki-Heck reactions under air in water and could be recycled without loss of activity.

  7. Using aqueous ammonia in hydroaminomethylation reactions: ruthenium-catalyzed synthesis of tertiary amines. (United States)

    Wu, Lipeng; Fleischer, Ivana; Zhang, Min; Liu, Qiang; Franke, Robert; Jackstell, Ralf; Beller, Matthias


    The direct synthesis of tertiary amines from ammonia and olefins is presented. Using a combination of Ru3 (CO)12 and 2-phosphino-substituted imidazole ligand as catalyst system allows for hydroaminomethylation reactions of bulk aliphatic and functionalized olefins. Tertiary amines are obtained in an atom-efficient domino process in moderate to good isolated yields (45-76%) with excellent regioselectivities (n/iso up to 99:1). © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. An Alternative Reaction Pathway for Iridium Catalyzed Water Oxidation Driven by CAN

    KAUST Repository

    Bucci, Alberto


    The generation of solar fuels by means of a photosynthetic apparatus strongly relies on the development of an efficient water oxidation catalyst (WOC). Cerium ammonium nitrate (CAN) is the most commonly used sacrificial oxidant to explore the potentiality of WOCs. It is usually assumed that CAN has the unique role to oxidatively energize WOCs, making them capable to offer a low energy reaction pathway to transform H2O to O2. Herein we show that CAN might have a much more relevant and direct role in WO, mainly related to the capture and liberation of O–O containing molecular moieties.

  9. Chiral Dawson-Type Hybrid Polyoxometalate Catalyzes Enantioselective Diels-Alder Reactions. (United States)

    Xuan, Wen-Jing; Botuha, Candice; Hasenknopf, Bernold; Thorimbert, Serge


    Can achiral organocatalysts linked to chiral polyanionic metal oxide clusters provide good selectivity in enantioselective C-C bond formations? The answer to this question is investigated by developing a new active hybrid polyoxometalate-based catalyst for asymmetric Diels-Alder reaction. Chirality transfer from the chiral anionic polyoxometalate to the covalently linked achiral imidazolidinone allows Diels-Alder cycloaddition products to be obtained with good yields and high enantioselectivities when using cyclopentadiene and acrylaldehydes as partners. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. A thermodynamic study of ketoreductase-catalyzed reactions 2. Reduction of cycloalkanones in non-aqueous solvents

    Energy Technology Data Exchange (ETDEWEB)

    Tewari, Yadu B. [Biotechnology Division, National Institute of Standards and Technology, Gaithersburg, MD 20899-8312 (United States)]. E-mail:; Phinney, Karen W. [Analytical Chemistry Division, National Institute of Standards and Technology, Gaithersburg, MD 20899-8312 (United States)]. E-mail:; Liebman, Joel F. [Department of Chemistry, University of Maryland, Baltimore County, Baltimore, MD 21250 (United States)]. E-mail:


    The equilibrium constants for the ketoreductase-catalyzed reactions (cycloalkanone+2-propanol=cycloalkanol+acetone) have been measured in n-hexane, n-pentane, and supercritical carbon dioxide SCCO{sub 2} (pressure=(8.0 to 12.0)MPa). The cycloalkanones included in this study were: cyclobutanone, cyclopentanone, cyclohexanone, cycloheptanone, and cyclooctanone. The equilibrium constants for the reactions involving cyclobutanone and cyclohexanone were measured in n-hexane over the range T=(288.35 to 308.05)K. The thermodynamic quantities at T=298.15K are: K=(0.763+/-0.001); {delta}{sub r}G{sub m}{sup -}bar =(0.670+/-0.002)kJ.mol{sup -1}; {delta}{sub r}H{sub m}{sup -}bar =-(1.09+/-0.11)kJ.mol{sup -1}, and {delta}{sub r}S{sub m}{sup -}bar =-(5.9+/-0.4)J.K{sup -1}.mol{sup -1} for the reaction involving cyclobutanone; and K=(15.7+/-0.2); {delta}{sub r}G{sub m}{sup -}bar =-(6.82+/-0.02)kJ.mol{sup -1}; {delta}{sub r}H{sub m}{sup -}bar =-(4.6+/-1.0)kJ.mol{sup -1}, and {delta}{sub r}S{sub m}{sup -}bar =(7.4+/-3.3)J.K{sup -1}.mol{sup -1} for the reaction involving cyclohexanone, respectively. An inspection of the equilibrium constants for these reactions in n-hexane, n-pentane, and SCCO{sub 2} shows that solvent dependence is not significant. The equilibrium constants of cycloalkanones decrease with increasing value of the number of carbons, N{sub C} with the exception of cyclohexanone. The cyclohexanol, which adopts a nearly strainless, idealized tetrahedral conformation around each carbon, is thermodynamically favored and more stable compared to other cycloalkanol rings, and this is reflected in the significantly higher value of the equilibrium constant obtained for this reaction. Comparisons with results obtained by using two independent thermochemical routes are also made.

  11. How low does iron go? Chasing the active species in fe-catalyzed cross-coupling reactions. (United States)

    Bedford, Robin B


    The catalytic cross-coupling reactions of organic halides or related substrates with organometallic nucleophiles form the cornerstone of many carbon-carbon bond-forming processes. While palladium-based catalysts typically mediate such reactions, there are increasing concerns about the long-term sustainability of palladium in synthesis. This is due to the high cost of palladium, coupled with its low natural abundance, environmentally deleterious extraction (∼6 g of metal are produced per ton of ore), toxicity, and competition for its use from the automotive and consumer electronics sectors. Therefore, there is a growing interest in replacing palladium-based catalysts with those incorporating more earth-abundant elements. With its low cost, high natural abundance, and low toxicity, iron makes a particularly appealing alternative, and accordingly, the development of iron-catalyzed cross-coupling is undergoing explosive growth. However, our understanding of the mechanisms that underpin the iron-based catalytic cycles is still very much in its infancy. Mechanistic insight into catalytic reactions is not only academically important but also allows us to maximize the efficiency of processes or even to develop entirely new transformations. Key to the development of robust mechanistic models for cross-coupling is knowing the lowest oxidation state in the cycle. Once this is established, we can explore subsequent redox processes and build the catalytic manifold. Until we know with confidence what the lowest oxidation state is, any cycles proposed are largely just guesswork. To date, Fe(-II), Fe(-I), Fe(0), Fe(I), and Fe(II) have been proposed as contenders for the lowest-oxidation-state species in the cycle in iron-catalyzed cross-coupling; the aim of this Account is to pull together the various pieces of evidence in support, or otherwise, of each of these suggestions in turn. There currently exists no direct evidence that oxidation states below Fe(0) are active in the

  12. A chemically modified lipase preparation for catalyzing the transesterification reaction in even highly polar organic solvents. (United States)

    Solanki, Kusum; Gupta, Munishwar Nath


    Acylation of Pseudomonas cepacia lipase with Pyromellitic dianhydride to modify 72% of total amino groups was carried out. Different organic solvents were screened for precipitation of modified lipase. It was found that 1,2-dimethoxyethane was the best precipitant which precipitated 97% protein and complete activity. PCMC (protein coated microcrystals), CLPCMC (crosslinked protein coated microcrystals), EPROS (enzyme precipitated and rinsed with organic solvents) and pH tuned preparations of modified and unmodified lipase were prepared and used for carrying out transesterification reaction with n-octane and dimethyl formamide (DMF) as reaction medium. In n-octane, among all the preparations, CLPCMC of modified lipase gave highest rate (1970 nmol min(-1)mg(-1)) as compared to unmodified pH tuned lipase (128 nmol min(-1) mg(-1)). In DMF, with both 1% (v/v) and 5% (v/v) water content, CLPCMC showed highest initial rate of 0.72 and 7.2 nmol min(-1) mg(-1), respectively. Unmodified pH tuned lipase showed no activity at all in DMF with both 1% and 5% (v/v) water content. Copyright © 2011 Elsevier Ltd. All rights reserved.

  13. Improved oxygen reduction reaction catalyzed by Pt/Clay/Nafion nanocomposite for PEM fuel cells. (United States)

    Narayanamoorthy, B; Datta, K K R; Eswaramoorthy, M; Balaji, S


    A novel Pt nanoparticle (Pt NP) embedded aminoclay/Nafion (Pt/AC/N) nanocomposite catalyst film was prepared for oxygen reduction reaction by sol-gel method. The prepared nanocomposite films were surface characterized using XRD and TEM and thermal stability was studied by TGA. The prepared film has firmly bound Pt NP and could exhibit an improved electro-reduction activity compared to vulcan carbon/Nafion supported Pt NP (Pt/VC/N). Moreover, the Pt/AC/N film possessed good stability in the acidic environment. The limiting current density of the Pt/AC/N film with 35.4 μg/cm(2) of Pt loading was found to be 4.2 mA/cm(2), which is 30% higher than that of the Pt/VC/N. The maximum H2O2 intermediate formation was found to be ∼1.6% and the reaction found to follow a four electron transfer mechanism. Accelerated durability test for 2000 potential cycles showed that ca. 78% of initial limiting current was retained. The results are encouraging for possible use of the Pt/AC/N as the free-standing electrocatalyst layer for polymer electrolyte membrane fuel cells.

  14. Mild Negishi cross-coupling reactions catalyzed by acenaphthoimidazolylidene palladium complexes at low catalyst loadings. (United States)

    Liu, Zelong; Dong, Ningning; Xu, Mizhi; Sun, Zheming; Tu, Tao


    Considering that the strong σ-donor property of ylidenes derived from π-extended imidazolium salts is conducive to increasing the catalytic activity of the resulting palladium N-heterocyclic carbene complexes, robust acenaphthoimidazol-ylidene palladium complexes 3a-c with varying bulky substituted groups were prepared from the corresponding acenaphthoimidazolium chlorides by heating with PdCl2 and K2CO3 in neat 3-chloropyridine in satisfactory yields. Even at a catalyst loading as low as 0.25 mol %, complex 3a exhibited extremely high catalytic activity toward Negishi cross-coupling of alkylzinc reagents with a wide range of (hetero)aryl halides under mild reaction conditions within 30 min. Besides a great number of bromoarenes, various less expensive and inactive (hetero)aryl chlorides were coupled successfully with the alkyl- and arylzinc reagents, in which active functional groups (such as -NH2) were well tolerated even in one-pot dicoupling transformations without protection. In addition, in the case of coupling with secondary alkylzinc reagents, undesired β-hydride elimination leading to isomerized linear products was efficaciously suppressed. The catalyst system also displayed superiority in the construction of heterobiaryls through the coupling of heteroarylzinc reagents and heterocylic chloroarenes which were hardly accessible from the corresponding organoboron reagents by Suzuki-coupling reactions. Therefore, the protocol described in this paper represents a mild, general, and scalable approach to access various structurally intriguing and functionalized (hetero)aryls.

  15. Chemical Reactions Catalyzed by Metalloporphyrin-Based Metal-Organic Frameworks

    Directory of Open Access Journals (Sweden)

    Kelly Aparecida Dias de Freitas Castro


    Full Text Available The synthetic versatility and the potential application of metalloporphyrins (MP in different fields have aroused researchers’ interest in studying these complexes, in an attempt to mimic biological systems such as cytochrome P-450. Over the last 40 years, synthetic MPs have been mainly used as catalysts for homogeneous or heterogeneous chemical reactions. To employ them in heterogeneous catalysis, chemists have prepared new MP-based solids by immobilizing MP onto rigid inorganic supports, a strategy that affords hybrid inorganic-organic materials. More recently, materials obtained by supramolecular assembly processes and containing MPs as building blocks have been applied in a variety of areas, like gas storage, photonic devices, separation, molecular sensing, magnets, and heterogeneous catalysis, among others. These coordination polymers, known as metal-organic frameworks (MOFs, contain organic ligands or complexes connected by metal ions or clusters, which give rise to a 1-, 2- or 3-D network. These kinds of materials presents large surface areas, Brønsted or redox sites, and high porosity, all of which are desirable features in catalysts with potential use in heterogeneous phases. Building MOFs based on MP is a good way to obtain solid catalysts that offer the advantages of bioinspired systems and zeolitic materials. In this mini review, we will adopt a historical approach to present the most relevant MP-based MOFs applicable to catalytic reactions such as oxidation, reduction, insertion of functional groups, and exchange of organic functions.

  16. Cycloaddition Reaction of Carbon Dioxide to Epoxides Catalyzed by Polymer-Supported Quaternary Phosphonium Salts

    Directory of Open Access Journals (Sweden)

    Yubing Xiong


    Full Text Available Polymer-supported quaternary phosphonium salt (PS-QPS was explored as effective catalyst for the coupling reaction of carbon dioxide with epoxides. The results indicated that cyclic carbonates with high yields (98.6% and excellent selectivity (100% could be prepared at the conditions of 5 MPa CO2, 150°C, and 6 h without the addition of organic solvents or cocatalysts. The effects of various reaction conditions on the catalytic performance were investigated in detail. The catalyst is applicable to a variety of epoxides, producing the corresponding cyclic carbonates in good yields. Furthermore, the catalyst could be recovered easily and reused for five times without loss of catalytic activity obviously. A proposed mechanism for synthesis of cyclic carbonate in the presence of PS-QPS was discussed. The catalyst was characterized by thermogravimetric analysis (TGA, scanning electron microscopy (SEM, and Fourier transform infrared (FT-IR spectrum. It is believed that PS-QPS is of great potential for CO2 fixation applications due to its unusual advantages, such as easy preparation, high activity and selectivity, stability, low cost, and reusability.

  17. Graphene oxide for acid catalyzed-reactions: Effect of drying process (United States)

    Gong, H. P.; Hua, W. M.; Yue, Y. H.; Gao, Z.


    Graphene oxides (GOs) were prepared by Hummers method through various drying processes, and characterized by XRD, SEM, FTIR, XPS and N2 adsorption. Their acidities were measured using potentiometric titration and acid-base titration. The catalytic properties were investigated in the alkylation of anisole with benzyl alcohol and transesterification of triacetin with methanol. GOs are active catalysts for both reaction, whose activity is greatly affected by their drying processes. Vacuum drying GO exhibits the best performance in transesterification while freezing drying GO is most active for alkylation. The excellent catalytic behavior comes from abundant surface acid sites as well as proper surface functional groups, which can be obtained by selecting appropriate drying process.

  18. Hydrolysis of inulin: a kinetic study of the reaction catalyzed by an inulinase from Aspergillus ficuum. (United States)

    Carniti, P; Beltrame, P L; Guardione, D; Focher, B; Marzetti, A


    A kinetic study of the hydrolysis of inulin was performed by using as catalyst a commercial inulinase from Aspergillus ficuum. The reaction was studied carrying out initial rate as well as time course measurements. Both inulinase and invertase activities of the enzyme were taken into account, and the corresponding kinetic parameters were determined in the temperature range 30-50 degrees C. The activation energies of the turnover constant for inulinase and invertase activities were found to be similar (56-57 kJ x mol(-1)). The ratio S/I of invertase to inulinase activity was 1.6 regardless of temperature. The thermal degradation of the enzyme was also investigated up to 70 degrees C, and an activation energy of 350-370 kJ x mol(-1) was evaluated.

  19. Bacteroides thetaiotaomicron VPI-5482 glycoside hydrolase family 66 homolog catalyzes dextranolytic and cyclization reactions. (United States)

    Kim, Young-Min; Yamamoto, Eiji; Kang, Min-Sun; Nakai, Hiroyuki; Saburi, Wataru; Okuyama, Masayuki; Mori, Haruhide; Funane, Kazumi; Momma, Mitsuru; Fujimoto, Zui; Kobayashi, Mikihiko; Kim, Doman; Kimura, Atsuo


    Bacteroides thetaiotaomicron VPI-5482 harbors a gene encoding a putative cycloisomaltooligosaccharide glucanotransferase (BT3087) belonging to glycoside hydrolase family 66. The goal of the present study was to characterize the catalytic properties of this enzyme. Therefore, we expressed BT3087 (recombinant endo-dextranase from Bacteroides thetaiotaomicron VPI-5482) in Escherichia coli and determined that recombinant endo-dextranase from Bacteroides thetaiotaomicron VPI-5482 preferentially synthesized isomaltotetraose and isomaltooligosaccharides (degree of polymerization > 4) from dextran. The enzyme also generated large cyclic isomaltooligosaccharides early in the reaction. We conclude that members of the glycoside hydrolase 66 family may be classified into three types: (a) endo-dextranases, (b) dextranases possessing weak cycloisomaltooligosaccharide glucanotransferase activity, and (c) cycloisomaltooligosaccharide glucanotransferases. © 2012 The Authors Journal compilation © 2012 FEBS.

  20. Palladium-catalyzed cross-coupling reactions of potassium alkenyltrifluoroborates with organic halides in aqueous media. (United States)

    Alacid, Emilio; Nájera, Carmen


    Potassium vinyl and alkenyltrifluoroborates are cross-coupled with aryl and heteroaryl bromides using 1 mol % Pd loading of 4-hydroxyacetophenone oxime derived palladacycle or Pd(OAc)2 as precatalysts, K2CO3 as base, and TBAB as additive and water reflux under conventional or microwave heating to afford styrenes, stilbenoids, and alkenylbenzenes. These borates can be cross-coupled diastereoselectively with allyl and benzyl chlorides using KOH as base in acetone-water (3:2) at 50 degrees C and 0.1 mol % Pd loading, giving the corresponding 1,4-dienes and allylarenes, respectively. These simple phosphine-free reaction conditions allow the palladium recycling from the aqueous phase during up to five runs by extractive separation of the products, which contain 58-105 ppm of Pd.

  1. Reply to Comment on "Enhanced diffusion of enzymes that catalyze exothermic reactions"

    CERN Document Server

    Golestanian, Ramin


    Catalytically active enzymes have recently been observed to exhibit enhanced diffusion. In a recent work [C. Riedel et al., Nature 517, 227 (2015)], it has been suggested that this phenomenon is correlated with the degree of exothermicity of the reaction, and a mechanism was proposed to explain the phenomenon based on channeling the released heat into the center of mass kinetic energy of the enzyme. I addressed this question by comparing four different mechanisms, and concluded that collective heating is the strongest candidate out of those four to explain the phenomenon, and in particular, several orders of magnitude stronger than the mechanism proposed by Riedel et al. In a recent preprint (arXiv:1608.05433), K. Tsekouras, C. Riedel, R. Gabizon, S. Marqusee, S. Presse, and C. Bustamante present a comment on my paper [R. Golestanian, Phys. Rev. Lett. 115, 108102 (2015); arXiv:1508.03219], which I address here in this reply.

  2. Synthesis of L-Ascorbyl Flurbiprofenate by Lipase-Catalyzed Esterification and Transesterification Reactions. (United States)

    Xin, Jia-Ying; Sun, Li-Rui; Chen, Shu-Ming; Wang, Yan; Xia, Chun-Gu


    The synthesis of L-ascorbyl flurbiprofenate was achieved by esterification and transesterification in nonaqueous organic medium with Novozym 435 lipase as biocatalyst. The conversion was greatly influenced by the kinds of organic solvents, speed of agitation, catalyst loading amount, reaction time, and molar ratio of acyl donor to L-ascorbic acid. A series of solvents were investigated, and tert-butanol was found to be the most suitable from the standpoint of the substrate solubility and the conversion for both the esterification and transesterification. When flurbiprofen was used as acyl donor, 61.0% of L-ascorbic acid was converted against 46.4% in the presence of flurbiprofen methyl ester. The optimal conversion of L-ascorbic acid was obtained when the initial molar ratio of acyl donor to ascorbic acid was 5 : 1. kinetics parameters were solved by Lineweaver-Burk equation under nonsubstrate inhibition condition. Since transesterification has lower conversion, from the standpoint of productivity and the amount of steps required, esterification is a better method compared to transesterification.

  3. Synthesis of L-Ascorbyl Flurbiprofenate by Lipase-Catalyzed Esterification and Transesterification Reactions

    Directory of Open Access Journals (Sweden)

    Jia-ying Xin


    Full Text Available The synthesis of L-ascorbyl flurbiprofenate was achieved by esterification and transesterification in nonaqueous organic medium with Novozym 435 lipase as biocatalyst. The conversion was greatly influenced by the kinds of organic solvents, speed of agitation, catalyst loading amount, reaction time, and molar ratio of acyl donor to L-ascorbic acid. A series of solvents were investigated, and tert-butanol was found to be the most suitable from the standpoint of the substrate solubility and the conversion for both the esterification and transesterification. When flurbiprofen was used as acyl donor, 61.0% of L-ascorbic acid was converted against 46.4% in the presence of flurbiprofen methyl ester. The optimal conversion of L-ascorbic acid was obtained when the initial molar ratio of acyl donor to ascorbic acid was 5 : 1. kinetics parameters were solved by Lineweaver-Burk equation under nonsubstrate inhibition condition. Since transesterification has lower conversion, from the standpoint of productivity and the amount of steps required, esterification is a better method compared to transesterification.

  4. Micelle-catalyzed reaction between ninhydrin and nickel dipeptide complex [Ni(II)-Gly-Tyr]+. (United States)

    Akram, Mohd; Kumar, Dileep; Kabir-ud-Din


    The interaction of nickel dipeptide complex [Ni(II)-Gly-Tyr](+) with ninhydrin has been investigated in the absence and presence of cationic cetyltrimethylammonium bromide (CTAB) and gemini (16-s-16, s=4, 5, 6) surfactants spectrophotometrically at 80°C and pH 5.0. The product formed was the same and the reaction followed first- and fractional-order kinetics with respect to [Ni(II)-Gly-Tyr](+) and [ninhydrin], respectively, in both aqueous as well as micellar media. In the presence of CTAB, rate increased and reached up to a maximum, then decreased. Also, whereas typical rate constant (k(Ψ)) increase and leveling-off regions, just like CTAB, were observed with geminis, the latter produced a third region of increasing k(Ψ) at higher concentrations. This unusual third-region effect of the gemini micelles is assigned to changes in their micellar morphologies. The micellar catalysis is explained in terms of pseudo-phase model. The binding constants and the values of activation parameters such as activation energy (E(a)), enthalpy of activation (ΔH(#)) and entropy of activation (ΔS(#)) have been evaluated. Copyright © 2012 Elsevier B.V. All rights reserved.

  5. Mission to Mars by catalyzed nuclear reactions of the commercialized cold fusion power

    Energy Technology Data Exchange (ETDEWEB)

    Woo, Tae Ho [Yonsei University, Wonju (Korea, Republic of)


    The chemical compound source is deficient to reach to the power as much as the journey to Mars, unless the massive equipment is installed like the nuclear fusion reactor. However, there is very significant limitations of making up the facility due to the propellant power. Therefore, the light and cheap energy source, Low energy nuclear reactions (LENRs), powered rocket has been proposed. In this paper, the power conditions by LENRs are analyzed. After the successful Apollo mission to Moon of the National Aeronautics and Space Administration (NASA) in the U.S. government, the civilian companies have proposed for the manned mission to Mars for the commercial journey purposes. The nuclear power has been a critical issue for the energy source in the travel, especially, by the LENR of LENUCO, Champaign, USA. As the velocity of the rocket increases, the mass flow rate decreases. It could be imaginable to take the reasonable velocity of spacecraft. The energy of the travel system is and will be created for the better one in economical and safe method. There is the imagination of boarding pass for spacecraft ticket shows the selected companies of cold fusion products. In order to solve the limitations of the conventional power sources like the chemical and solar energies, it is reasonable to design LENR concept. Since the economical and safe spacecraft is very important in the long journey on and beyond the Mars orbit, a new energy source, LENR, should be studied much more.

  6. Kinetic modeling of lipase-catalyzed esterification reaction between oleic acid and trimethylolpropane: a simplified model for multi-substrate multi-product ping-pong mechanisms. (United States)

    Bornadel, Amin; Akerman, Cecilia Orellana; Adlercreutz, Patrick; Hatti-Kaul, Rajni; Borg, Niklas


    Kinetic models are among the tools that can be used for optimization of biocatalytic reactions as well as for facilitating process design and upscaling in order to improve productivity and economy of these processes. Mechanism pathways for multi-substrate multi-product enzyme-catalyzed reactions can become very complex and lead to kinetic models comprising several tens of terms. Hence the models comprise too many parameters, which are in general highly correlated and their estimations are often prone to huge errors. In this study, Novozym(®) 435 catalyzed esterification reaction between oleic acid (OA) and trimethylolpropane (TMP) with continuous removal of side-product (water) was carried out as an example for reactions that follow multi-substrate multi-product ping-pong mechanisms. A kinetic model was developed based on a simplified ping-pong mechanism proposed for the reaction. The model considered both enzymatic and spontaneous reactions involved and also the effect of product removal during the reaction. The kinetic model parameters were estimated using nonlinear curve fitting through unconstrained optimization methodology and the model was verified by using empirical data from different experiments and showed good predictability of the reaction under different conditions. This approach can be applied to similar biocatalytic processes to facilitate their optimization and design. © 2013 American Institute of Chemical Engineers.

  7. Pd-catalyzed ethylene methoxycarbonylation with Brønsted acid ionic liquids as promoter and phase-separable reaction media

    DEFF Research Database (Denmark)

    Garcia-Suarez, Eduardo J.; Khokarale, Santosh Govind; Nguyen van Buu, Olivier


    .g. methanesulfonic acid or sulfuric acid, resulting in high catalytic activity and selectivity towards methyl propionate. In addition, the BAILs yielded a biphasic system with the product and provided stability to palladium intermediates avoiding the undesirable formation of palladium black after reaction......Brønsted acid ionic liquids (BAILs) were prepared and applied as combined acid promoters and reaction media in Pd–phosphine catalyzed methoxycarbonylation of ethylene to produce methyl propionate. The BAILs served as alternatives to common mineral acids required for the reaction, e...

  8. Hydrodesulfurization of dibenzothiophene catalyzed by sulfided CoO-MoO/sub 3/. gamma. -Al/sub 2/O/sub 3/: the reaction network. [Dibenzothiophene

    Energy Technology Data Exchange (ETDEWEB)

    Houalla, M.; Nag, N.K.; Sapre, A.V.; Broderick, D.H.; Gates, B.C.


    Kinetic experiments in a high-pressure microreactor and a batch autoclave reactor elucidated the reaction network in the hydrodesulfurization of dibenzothiophene (a relatively unreactive compound in petroleum and coal-derived liquids), catalyzed by sulfided cobalt oxide/molybdenum trioxide/..gamma..-alumina at 573/sup 0/K and 102 atm. The predominant reaction was a direct sulfur extrusion, giving biphenyl and hydrogen sulfide; the biphenyl was subsequently hydrogenated slowly to give cyclohexylbenzene and then bicyclohexyl. Dibenzothiophene also underwent a primary hydrogenation reaction preceding sulfur removal, but it was about 1000 times slower than the sulfur extrusion reaction. The results showed that when methyl groups are present in the four and six positions of dibenzothiophene, the primary hydrogenation reaction is approximately as fast as the primary hydrodesulfurization reaction. Nickel and molybdenum or nickel and tungsten used instead of cobalt and molybdenum in the catalyst, or hydrogen sulfide in the reactant mixture, also favor hydrogenation relative to hydrodesulfurization.

  9. A Zinc Catalyzed C(sp(3) )-C(sp(2) ) Suzuki-Miyaura Cross-Coupling Reaction Mediated by Aryl-Zincates. (United States)

    Procter, Richard J; Dunsford, Jay J; Rushworth, Philip J; Hulcoop, David G; Layfield, Richard A; Ingleson, Michael J


    The Suzuki-Miyaura (SM) reaction is one of the most important methods for C-C bond formation in chemical synthesis. In this communication, we show for the first time that the low toxicity, inexpensive element zinc is able to catalyze SM reactions. The cross-coupling of benzyl bromides with aryl borates is catalyzed by ZnBr2 , in a process that is free from added ligand, and is compatible with a range of functionalized benzyl bromides and arylboronic acid pinacol esters. Initial mechanistic investigations indicate that the selective in situ formation of triaryl zincates is crucial to promote selective cross-coupling reactivity, which is facilitated by employing an arylborate of optimal nucleophilicity. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Computational studies on the regioselectivity of metal-catalyzed synthesis of 1,2,3 triazoles via click reaction: a review. (United States)

    Hosseinnejad, Tayebeh; Fattahi, Bahareh; Heravi, Majid M


    Recently, the experimental and computational chemists have been attracted widely to the click synthesis of 1,2,3 triazoles and their derivatives, mainly due to the fact that they are interesting from structural and mechanistic points of view. Moreover, catalyzed click have been well established as a successful strategy showing high regioselectivity and high yield for the synthesis of 1,2,3-triazoles. In this review, we try to highlight the recently reported computational assessments on the origins and predection of regioselectivity in the catalyzed click synthesis of triazoles from the mechanistic and thermodynamical points of view. In this light, density functional theory (DFT) calculations on the free energy profiles of azide-alkyne cycloaddition reactions have been underscored. The stereoelectronic features for the role of copper, ruthenium, and iridium as catalyst on regioselectivity of click reactions have also be discussed. Graphical Abstract Computational origins for the regioselective behavior of 1,2,3 triazoles click synthesis.

  11. Sonogashira Reaction of Aryl and Heteroaryl Halides with Terminal Alkynes Catalyzed by a Highly Efficient and Recyclable Nanosized MCM-41 Anchored Palladium Bipyridyl Complex

    Directory of Open Access Journals (Sweden)

    Chung-Yuan Mou


    Full Text Available A heterogeneous catalyst, nanosized MCM-41-Pd, was used to catalyze the Sonogashira coupling of aryl and heteroaryl halides with terminal alkynes in the presence of CuI and triphenylphosphine. The coupling products were obtained in high yields using low Pd loadings to 0.01 mol%, and the nanosized MCM-41-Pd catalyst was recovered by centrifugation of the reaction solution and re-used in further runs without significant loss of reactivity.

  12. Visible-Light Photoredox-Catalyzed Giese Reaction: Decarboxylative Addition of Amino Acid Derived α-Amino Radicals to Electron-Deficient Olefins

    KAUST Repository

    Millet, Anthony


    A tin- and halide-free, visible-light photoredox-catalyzed Giese reaction was developed. Primary and secondary α-amino radicals were generated readily from amino acids in the presence of catalytic amounts of an iridium photocatalyst. The reactivity of the α-amino radicals has been evaluated for the functionalization of a variety of activated olefins. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

  13. Synthesis of quinazolines and tetrahydroquinazolines: copper-catalyzed tandem reactions of 2-bromobenzyl bromides with aldehydes and aqueous ammonia or amines. (United States)

    Fan, Xuesen; Li, Bin; Guo, Shenghai; Wang, Yuanyuan; Zhang, Xinying


    An efficient synthesis of diversely substituted quinazolines and 1,2,3,4-tetrahydroquinazolines through copper-catalyzed tandem reactions of the readily available 2-bromobenzyl bromides, aldehydes, and aqueous ammonia or amines has been developed. By using ammonia and simple aliphatic amines as the nitrogen source, the present method provides a versatile and practical protocol for the synthesis of quinazolines and 1,2,3,4-tetrahydroquinazolines. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Theoretical Study of the Phosphoryl Transfer Reaction from ATP to Dha Catalyzed by DhaK from Escherichia coli. (United States)

    Bordes, I; Castillo, R; Moliner, V


    Protein kinases, representing one of the largest protein families involved in almost all aspects of cell life, have become one of the most important targets for the development of new drugs to be used in, for instance, cancer treatments. In this article an exhaustive theoretical study of the phosphoryl transfer reaction from adenosine triphosphate (ATP) to dihydroxyacetone (Dha) catalyzed by DhaK from Escherichia coli (E. coli) is reported. Two different mechanisms, previously proposed for the phosphoryl transfer from ATP to the hydroxyl side chain of specific serine, threonine, or tyrosine residues, have been explored based on the generation of free energy surfaces (FES) computed with hybrid QM/MM potentials. The results suggest that the substrate-assisted phosphoryl and proton-transfer mechanism is kinetically more favorable than the mechanism where an aspartate would be activating the Dha. Although the details of the mechanisms appear to be dramatically dependent on the level of theory employed in the calculations (PM3/MM, B3LYP:PM3/MM, or B3LYP/MM), the transition states (TSs) for the phosphoryl transfer step appear to be described as a concerted step with different degrees of synchronicity in the breaking and forming bonds process in both explored mechanisms. Residues of the active site belonging to different subunits of the protein, such as Gly78B, Thr79A, Ser80A, Arg178B, and one Mg(2+) cation, would be stabilizing the transferred phosphate in the TS. Asp109A would have a structural role by posing the Dha and other residues of the active site in the proper orientation. The information derived from our calculations not only reveals the role of the enzyme and the particular residues of its active site, but it can assist in the rational design of new more specific inhibitors.

  15. Evidence for a transient peroxynitro acid in the reaction catalyzed by nitronate monooxygenase with propionate 3-nitronate. (United States)

    Smitherman, Crystal; Gadda, Giovanni


    Nitronate monooxygenase is a flavin-dependent enzyme that catalyzes the denitrification of propionate 3-nitronate (P3N) and other alkyl nitronates. The enzyme was previously known as 2-nitropropane dioxygenase, until its reclassification in 2010 by the IUBMB. Physiologically, the monooxygenase from fungi protects the organism from the environmental occurrence of P3N, which shuts down the Krebs cycle by inactivating succinate dehydrogenase and fumarase. The inhibition of these enzymes yields severe neurological disorders or death. Here, we have used for the first time steady-state and rapid kinetics, viscosity and pH effects, and time-resolved absorbance spectroscopy of the enzyme in turnover with P3N and the substrate analogue ethyl nitronate (EN) to elucidate the mechanism of the reaction. A transient increase in absorbance at ∼300 nm, never reported before, was seen during steady-state turnover of the enzyme with P3N and oxygen, with no concomitant changes between 400 and 600 nm. The transient species was not detected when oxygen was absent. Anaerobic reduction of the enzyme with P3N yielded anionic flavosemiquinone and was fast (e.g., ≥1900 s(-1)). Steady-state kinetics demonstrated that oxygen reacts before the release of the product of P3N oxidation from the enzyme. No pH effects were seen with P3N on kcat/Km, kcat/Koxygen, and kcat; in contrast, with EN, the kcat/Km and kcat decreased with increasing pH defining two plateaus and a pKa ∼ 8.0. Solvent viscosity at the pH optima suggested product release as being partially controlling the overall rate of turnover with the physiological substrate and its analogue. A mechanism that satisfies the kinetic results is proposed.

  16. Mechanism of the orotidine 5'-monophosphate decarboxylase-catalyzed reaction: importance of residues in the orotate binding site. (United States)

    Iiams, Vanessa; Desai, Bijoy J; Fedorov, Alexander A; Fedorov, Elena V; Almo, Steven C; Gerlt, John A


    The reaction catalyzed by orotidine 5'-monophosphate decarboxylase (OMPDC) is accompanied by exceptional values for rate enhancement (k(cat)/k(non) = 7.1 × 10(16)) and catalytic proficiency [(k(cat)/K(M))/k(non) = 4.8 × 10(22) M(-1)]. Although a stabilized vinyl carbanion/carbene intermediate is located on the reaction coordinate, the structural strategies by which the reduction in the activation energy barrier is realized remain incompletely understood. This laboratory recently reported that "substrate destabilization" by Asp 70 in the OMPDC from Methanothermobacter thermoautotrophicus (MtOMPDC) lowers the activation energy barrier by ∼5 kcal/mol (contributing ~2.7 × 10(3) to the rate enhancement) [Chan, K. K., Wood, B. M., Fedorov, A. A., Fedorov, E. V., Imker, H. J., Amyes, T. L., Richard, J. P., Almo, S. C., and Gerlt, J. A. (2009) Biochemistry 48, 5518-5531]. We now report that substitutions of hydrophobic residues in a pocket proximal to the carboxylate group of the substrate (Ile 96, Leu 123, and Val 155) with neutral hydrophilic residues decrease the value of k(cat) by as much as 400-fold but have a minimal effect on the value of k(ex) for exchange of H6 of the FUMP product analogue with solvent deuterium; we hypothesize that this pocket destabilizes the substrate by preventing hydration of the substrate carboxylate group. We also report that substitutions of Ser 127 that is proximal to O4 of the orotate ring decrease the value of k(cat)/K(M), with the S127P substitution that eliminates hydrogen bonding interactions with O4 producing a 2.5 × 10(6)-fold reduction; this effect is consistent with delocalization of the negative charge of the carbanionic intermediate on O4 that produces an anionic carbene intermediate and thereby provides a structural strategy for stabilization of the intermediate. These observations provide additional information about the identities of the active site residues that contribute to the rate enhancement and, therefore

  17. A Sequential Indium-Mediated Aldehyde Allylation/Palladium-Catalyzed Cross-Coupling Reaction in the Synthesis of 2-Deoxy-β-C-Aryl Glycosides (United States)

    Moral, John Alec; Moon, Seong-Jin; Rodriguez-Torres, Samuel; Minehan, Thomas G.


    Indium-mediated allylation of aldehydes with 2-chloro-3-iodopropene, followed by a palladium-catalyzed cross-coupling reaction with triarylindium reagents or arylboronic acids, leads to aryl-substituted homoallylic alcohols in good to excellent yields and diastereoselectivities. The products obtained from reactions conducted with D-glyceraldehyde acetonide can be transformed into 2-deoxy-β-C-aryl ribofuranosides in high overall yields. Similarly, 2-deoxy-β-C-aryl allopyranosides may be prepared efficiently from 2,4-O-benzylidene erythrose. PMID:19630430

  18. Functionalization of Azacalixaromatics by Cu(II)-Catalyzed Oxidative Cross-Coupling Reaction between the Arene C-H Bond and Boronic Acids. (United States)

    Liu, Yang; Long, Chao; Zhao, Liang; Wang, Mei-Xiang


    Catalyzed by Cu(ClO4)2·6H2O under mild aerobic conditions using air as the oxidant, azacalix[1]arene[3]pyridines underwent a highly efficient oxidative cross-coupling reaction with a large number of aryl-, alkenyl-, and alkylboronic acids to afford diverse functionalized macrocycles. Stoichiometric reactions of an arylboronic acid with isolated and structurally well-defined high valent organocopper compounds indicated the involvement of arylcopper(II) rather than arylcopper(III) species as an organometallic intermediate in catalysis.

  19. One-Pot Synthesis of Novel Chiral β-Amino Acid Derivatives by Enantioselective Mannich Reactions Catalyzed by Squaramide Cinchona Alkaloids

    Directory of Open Access Journals (Sweden)

    Kankan Zhang


    Full Text Available An efficient one-pot synthesis of novel β-amino acid derivatives containing a thiadiazole moiety was developed using a chiral squaramide cinchona alkaloid as organocatalyst. The reactions afforded chiral β-amino acid derivatives in moderate yields and with moderate to excellent enantioselectivities. The present study demonstrated for the first time the use of a Mannich reaction catalyzed by a chiral bifunctional organocatalyst for the one-pot synthesis of novel β-amino acid derivatives bearing a 1,3,4-thiadiazole moiety on nitrogen.

  20. Visible-light-induced, Ir-catalyzed reactions of N-methyl-N-((trimethylsilylmethylaniline with cyclic α,β-unsaturated carbonyl compounds

    Directory of Open Access Journals (Sweden)

    Dominik Lenhart


    Full Text Available N-Methyl-N-((trimethylsilylmethylaniline was employed as reagent in visible-light-induced, iridium-catalyzed addition reactions to cyclic α,β-unsaturated carbonyl compounds. Typical reaction conditions included the use of one equivalent of the reaction substrate, 1.5 equivalents of the aniline and 2.5 mol % (in MeOH or 1.0 mol % (in CH2Cl2 [Ir(ppy2(dtbbpy]BF4 as the catalyst. Two major reaction products were obtained in combined yields of 30–67%. One product resulted from aminomethyl radical addition, the other product was a tricyclic compound, which is likely formed by attack of the intermediately formed α-carbonyl radical at the phenyl ring. For five-membered α,β-unsaturated lactone and lactam substrates, the latter products were the only products isolated. For the six-membered lactones and lactams and for cyclopentenone the simple addition products prevailed.

  1. Reaction Mechanisms of CO2 Reduction to Formaldehyde Catalyzed by Hourglass Ru, Fe, and Os Complexes: A Density Functional Theory Study

    Directory of Open Access Journals (Sweden)

    Chunhua Dong


    Full Text Available The reaction mechanisms for the reduction of carbon dioxide to formaldehyde catalyzed by bis(tricyclopentylphosphine metal complexes, [RuH2(H2(PCyp32] (1Ru, [FeH2(H2(PCyp32] (1Fe and [OsH4(PCyp32] (1Os, were studied computationally by using the density functional theory (DFT. 1Ru is a recently reported highly efficient catalyst for this reaction. 1Fe and 1Os are two analogues of 1Ru with the Ru atom replaced by Fe and Os, respectively. The total free energy barriers of the reactions catalyzed by 1Ru, 1Fe and 1Os are 24.2, 24.0 and 29.0 kcal/mol, respectively. With a barrier close to the experimentally observed Ru complex, the newly proposed iron complex is a potential low-cost catalyst for the reduction of carbon dioxide to formaldehyde under mild conditions. The electronic structures of intermediates and transition states in these reactions were analyzed by using the natural bond orbital theory.

  2. Rhodium Catalyzed Decarbonylation

    DEFF Research Database (Denmark)

    Garcia Suárez, Eduardo José; Kahr, Klara; Riisager, Anders


    Rhodium catalyzed decarbonylation has developed significantly over the last 50 years and resulted in a wide range of reported catalyst systems and reaction protocols. Besides experimental data, literature also includes mechanistic studies incorporating Hammett methods, analysis of kinetic isotope...... effects as well as computational studies of model systems, which give an indication of the scope of the process. In this chapter, fundamental applications of Rh-catalyzed decarbonylation reactions are surveyed and discussed, including cross-coupling reactions, tandem reactions, and alternative...

  3. Spectroscopic Analyses on Reaction Intermediates Formed during Chlorination of Alkanes with NaOCl Catalyzed by a Nickel Complex

    NARCIS (Netherlands)

    Draksharapu, Apparao; Codolà, Zoel; Gómez, Laura; Lloret-Fillol, Julio; Browne, Wesley R; Costas, Miquel


    The spectroscopic, electrochemical, and crystallographic characterization of [((Me,H)PyTACN)Ni(II)(CH3CN)2](OTf)2 (1) ((Me,H)PyTACN = 1-(2-pyridylmethyl)-4,7-dimethyl-1,4,7-triazacyclononane, OTf = CF3SO3) is described together with its reactivity with NaOCl. 1 catalyzes the chlorination of alkanes

  4. Assessment of the Full Compatibility of Copper(I)-Catalyzed Alkyne-Azide Cycloaddition and Oxime Click Reactions for bis-Labelling of Oligonucleotides. (United States)

    Estalayo-Adriàn, Sandra; Lartia, Rémy; Meyer, Albert; Vasseur, Jean-Jacques; Morvan, François; Defrancq, Eric


    The conjugation of oligonucleotides with reporters is of great interest for improving their intrinsic properties or endowing new ones. In this context, we report herein a new procedure for the bis-labelling of oligonucleotides through oxime ligation (Click-O) and copper(I)-catalyzed alkyne-azide cycloaddition (Click-H). 5'-Azido and 3'-aldehyde precursors were incorporated into oligonucleotides, and subsequent coupling reactions through Click-O and Click-H (or vice versa) were successfully achieved. In particular, we exhaustively investigated the full compatibility of each required step for both tethering strategies. The results demonstrate that click Huisgen and click oxime reactions are fully compatible. However, whilst both approaches can deliver the targeted doubly conjugated oligonucleotide, the route involving click oxime ligation prior to click Huisgen is significantly more successful. Thus the reactions investigated here can be considered to be key elements of the chemical toolbox for the synthesis of highly sophisticated bioconjugates.

  5. Four mechanisms in the reactions of 3-aminopyrrole with 1,3,5-triazines: inverse electron demand Diels-Alder cycloadditions vs S(N)Ar reactions via uncatalyzed and acid-catalyzed pathways. (United States)

    De Rosa, Michael; Arnold, David; Hartline, Douglas


    Reaction of 3-aminopyrrole with seven 1,3,5-triazines was studied in a one-step reaction (in situ formation of 3-aminopyrrole) and a two-step reaction (using the tetraphenylborate salt and an amine base). An inverse-electron demand Diels-Alder reaction (IEDDA) was observed with R1 = CF3, CO2Et, and H with the formation of 5H-pyrrolo[3,2-d]pyrimidine derivatives. S(N)Ar was observed when 2,4,6-trifluoro- or 2,4,6-trichloro-1,3,5-triazine were used--1,3,5-triazines that had leaving groups. If excess 1,3,5-triazine was present the initial S(N)Ar product reacted further, in the presence of acid and water, with another equivalent of 1,3,5-triazine to give compounds containing three linked heterocyclic rings. No reaction was observed with R1 = C6H5 and OCH3. Four mechanisms are proposed to explain the experimental results: uncatalyzed and acid catalyzed inverse electron demand Diels-Alder cascades leading to cycloaddition, and uncatalyzed and acid-catalyzed S(N)Ar reactions leading, respectively, to single and double substitution products. Acid catalysis was a factor when there was reduced reactivity in either reactant.

  6. New approach to the preparation of bicyclo octane derivatives via the enantioselective cascade reaction catalyzed by chiral diamine-Ni(OAc)2 complex. (United States)

    Li, Wenyi; Liu, Xiaodong; Mao, Zhifeng; Chen, Qiao; Wang, Rui


    A highly efficient catalyst system assembled from enantiomerically pure diaminocyclohexane and Ni(OAc)(2) is, for the first time, used to catalyze the cascade Michael-Henry reaction of various diones and substituted nitroalkenes. A series of polyfunctionalized bicyclo[3.2.1]octane derivatives containing four stereogenic centers are prepared with excellent enantioselectivities (up to >99% ee) and diastereoselectivities (up to 50 : 1 dr) with high yields. In addition, via this chiral diamine-Ni(OAc)(2) catalyst system, the base-induced epimerization leading to the decrease of stereoselectivity can be prevented.

  7. Palladium-catalyzed Kumada coupling reaction of bromoporphyrins with silylmethyl Grignard reagents: preparation of silylmethyl-substituted porphyrins as a multipurpose synthon for fabrication of porphyrin systems. (United States)

    Sugita, Noriaki; Hayashi, Satoshi; Hino, Fumio; Takanami, Toshikatsu


    We have developed an efficient method for preparing silylmethyl-substituted porphyrins via the palladium-catalyzed Kumada cross-coupling reaction of bromoporphyrins with silylmethyl Grignard reagents. We demonstrated the synthetic utility of these silylmethylporphyrins as a multipurpose synthon for fabricating porphyrin derivatives through a variety of transformations of the silylmethyl groups, including the DDQ-promoted oxidative conversion to CHO, CH(2)OH, CH(2)OMe, and CH(2)F functionalities and the fluoride ion-mediated desilylative introduction of carbon-carbon single and double bonds.

  8. Lanthanide (III)-catalyzed enantioselective Diels-Alder reactions. Stereoselective synthesis of both enantiomers by using a single chiral source and a choice of achiral ligands

    Energy Technology Data Exchange (ETDEWEB)

    Kobayashi, Shu; Ishitani, Haruro (Science Univ. of Tokyo (Japan))


    In this paper, we disclose a conceptually different approach to obtaining both enantiomers; choice of enatiofacial selectivity by use of the enatiomerically same chiral source and different achiral ligands. Both enantiomers of the Diels-Alder adducts between e-acyl-1,3-oxazolidin-2-ones and cyclopentadiene were prepared by chiral lanthanides(III)-catalyzed reactions using the same chiral source, (R)-(+)-binaphthol. It is noted that the chiral catalysts with reverse enantiofacial selectivities could be prepared by using the same chiral source and a choice of achiral ligands. 14 refs., 3 tabs.

  9. Copper-catalyzed retro-aldol reaction of β-hydroxy ketones or nitriles with aldehydes: chemo- and stereoselective access to (E)-enones and (E)-acrylonitriles. (United States)

    Zhang, Song-Lin; Deng, Zhu-Qin


    A copper-catalyzed transfer aldol type reaction of β-hydroxy ketones or nitriles with aldehydes is reported, which enables chemo- and stereoselective access to (E)-α,β-unsaturated ketones and (E)-acrylonitriles. A key step of the in situ copper(i)-promoted retro-aldol reaction of β-hydroxy ketones or nitriles is proposed to generate a reactive Cu(i) enolate or cyanomethyl intermediate, which undergoes ensuing aldol condensation with aldehydes to deliver the products. This reaction uses 1.2 mol% Cu(IPr)Cl (IPr denotes 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) as the catalyst in the presence of 6.0 mol% NaOtBu cocatalyst at room temperature or 70 °C. A range of aryl and heteroaryl aldehydes as well as acrylaldehydes are compatible with many useful functional groups being tolerated. Under the mild and weakly basic conditions, competitive Cannizzaro-type reaction of benzaldehydes and side reactions of base-sensitive functional groups can be effectively suppressed, which show synthetic advantages of this reaction compared to classic aldol reactions. The synthetic potential of this reaction is further demonstrated by the one-step synthesis of biologically active quinolines and 1,8-naphthyridine in excellent yields (up to 91%). Finally, a full catalytic cycle for this reaction has been constructed using DFT computational studies in the context of a retro-aldol/aldol two-stage mechanism. A rather flat reaction energy profile is found indicating that both stages are kinetically facile, which is consistent with the mild reaction conditions.

  10. A copper-catalyzed reaction of oximes with diisopropyl azodicarboxylate: an alternative method for the synthesis of oxime carbonates. (United States)

    Usman, Muhammad; Ren, Zhi-Hui; Wang, Yao-Yu; Guan, Zheng-Hui


    A new Cu-catalyzed efficient protocol is described for the transformation of oximes to the corresponding carbonate derivatives. Diisopropyl azodicarboxylate acted as a selective new precursor for the synthesis of oxime carbonates in high yields. The O-H bond cleavage and O-C bond formation occur in the presence of a copper catalyst providing a synthetically useful process, which tolerates a wide range of functional groups.

  11. Palladium-Catalyzed One-Pot Reaction of Hydrazones, Dihaloarenes, and Organoboron Reagents: Synthesis and Cytotoxic Activity of 1,1-Diarylethylene Derivatives. (United States)

    Roche, Maxime; Salim, Salim Mmadi; Bignon, Jérôme; Levaique, Hélène; Brion, Jean-Daniel; Alami, Mouad; Hamze, Abdallah


    A new three-component assembly reaction between N-tosylhydrazones, dihalogenated arenes, and boronic acids or boronate esters was developed, producing highly substituted 1,1-diarylethylenes in good yields. The two C-C bonds formed through this coupling have been catalyzed by a single Pd-catalyst in a one-pot fashion. It is noted that the one-pot pinacol boronate cross-coupling reaction generally provides products in high yields, offers an expansive substrate scope, and can address a broad range of aryl, styrene, vinyl, and heterocyclic olefinic targets. The scope of this one-pot coupling has been also extended to the synthesis of the 1,1-diarylethylene skeleton of the natural product ratanhine. The new compounds were evaluated for their cytotoxic activity, and this allowed the identification of compound 4ab that exhibits excellent antiproliferative activity in the nanomolar concentration range against HCT116 cancer cell lines.

  12. A concise synthesis of substituted stilbenes and styrenes from propargylic phosphonium salts by a cobalt-catalyzed Diels-Alder/Wittig olefination reaction sequence. (United States)

    Hilt, Gerhard; Hengst, Christoph


    The cobalt(I)-catalyzed Diels-Alder reaction of propargylic phosphonium salts and longer chained alkyne-functionalized phosphonium salts with 1,3-dienes led to dihydroaromatic phosphonium salt intermediates which were directly used in a one-pot Wittig-type olefination reaction with aldehydes. Subsequent oxidation led to styrene- and stilbene-type products under formation of three new carbon-carbon bonds in a single synthetical step starting from three variable starting materials. The E/Z stereoselectivities of the products revealed that the dihydroaromatic phosphonium ylides behave as semistabilized ylides giving predominantly the E-configured products. The application of unsymmetrical 1,3-dienes as well as internal phosphonium functionalized alkynes is also described.

  13. Copper-catalyzed Huisgen cycloaddition reactions used to incorporate NLO chromophores into high Tg Side-Chain Polymers for Electro-Optics (United States)

    Liu, Jialei; Si, Peng; Liu, Xinhou; Zhen, Zhen


    Polymers based on N-phenyl maleimide, N-4-propargyl methoxy phenyl maleimide and methyl methacrylate was synthesized. High glass temperatures 183, 179, 159 °C respectively for P1, P2 and P3 were achieved. EO polymer P3-C1, P3-C2 and P3-C3 with about 30 wt% chromophore loading density were prepared by attaching Chromophore C1, C2 and C3 to polymer P3 using copper-catalyzed Huisgen cycloaddition reactions in mild reaction conditions and high yield. Among the EO polymers, P3-C3 showed us the best solubility in normal solvents and suitable glass temperature. EO films based on EO polymer P3-C3 showed us large EO coefficient of 50 pm/V @1310 nm and good long-term stability, 85% EO activity was kept after annealing at 85 °C for 200 h.

  14. Copper(I)-Catalyzed Asymmetric Desymmetrization through Inverse-Electron-Demand aza-Diels-Alder Reaction: Efficient Access to Tetrahydropyridazines Bearing a Unique α-Chiral Silane Moiety. (United States)

    Wei, Liang; Zhou, Yu; Song, Zhi-Min; Tao, Hai-Yan; Lin, Zhenyang; Wang, Chun-Jiang


    An unprecedented copper(I)-catalyzed asymmetric desymmetrization of 5-silylcyclopentadienes with in situ formed azoalkene was realized through an inverse-electron-demand aza-Diels-Alder reaction (IEDDA) pathway, in which 5-silylcyclopentadienes served as efficient enophiles. This new protocol provides a facile access to the biologically important heterocyclic tetrahydropyridazines containing a unique α-chiral silane motif and three adjoining stereogenic centers in generally good yield (up to 92 %) with exclusive regioselectivity, high diastereoselectivity (>20:1 diastereomeric ratio), and excellent enantioselectivity (up to 98 % enantiomeric excess). DFT calculations and control experiments further confirmed the proposed reaction mechanism. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Theoretical Mechanism Studies on the Enantioselectivity of aza-MBH-type Reaction of Nitroalkene to N-tosylimine Catalyzed by Thiourea-tertiary Amine

    Energy Technology Data Exchange (ETDEWEB)

    Lu, Nan; Wang, Huatian; Wang, Yangping [Shandong Agricultural Univ., Taian (China)


    The enantioselective aza-Morita Baylis Hillman reaction of nitroalkene and N-tosylimine catalyzed by thiourea-tertiary amine has been investigated using density functional theory. Enantioselectivity is dominated by the cooperative effect of non-covalent and weak covalent interactions imposed by different units of catalyst. As Lewis base, the tertiary amine unit activates nitroalkene via weak covalent bond. The weak covalent interaction orients the reaction in a major path with smaller variations of this bond. The aromatic ring unit activates N-tosylimine via π-π stacking. The non-covalent interaction selects the major path with smaller changes of the efficient packing areas. Thiourea unit donates more compact H-bonded network for species of the major path. The calculated ee value in xylene solution phase (97.6%) is much higher than that in N,N-Dimethylformamide (27.2%). Our conclusion is also supported by NBO analysis.

  16. Investigation of Pd-catalyzed Co(III-EDTA/hypophosphite inhibition reaction kinetics, mechanism and the evaluation of its analytical application possibilities

    Directory of Open Access Journals (Sweden)

    M. AKCAY


    Full Text Available The reaction between Co(III-EDTA and hypophosphite ion, catalyzed by Pd(II was chosen as the indicator reaction. The inhibition kinetics of this catalytic reaction have been investigated by a mechanistic approach in the presence of some inhibitors. Catalysts other than PdCl2, that is Pt, Au, Ni salts, did not exhibit any effect on the reaction. An original reaction mechanism is proposed based on the experimental data. The important variables were optimized for maximum sensitivity. The calibration graph, which was prepared following the inhibition kinetic method, showed a linear relationship (r = – 0.9878 between the initial rate and iodide in the concentration range of 2–35 ng/cm3 I- with a detection limit of 1.2 ng/cm3 I- (3Sb/m criterion. The RSDs of the method, (N = 5 for 7 and 14 ng/cm3 were 1.19 and 0.81 %, respectively, depended on iodide concentration. The method was only applied to the determination of iodide in water, urine, iodized table salt and some drug samples and was compared with the modified Sandell–Kolthoff method.

  17. [3,3]-Sigmatropic rearrangement versus carbene formation in gold-catalyzed transformations of alkynyl aryl sulfoxides: mechanistic studies and expanded reaction scope. (United States)

    Lu, Biao; Li, Yuxue; Wang, Youliang; Aue, Donald H; Luo, Yingdong; Zhang, Liming


    Gold-catalyzed intramolecular oxidation of terminal alkynes with an arenesulfinyl group as the tethered oxidant is a reaction of high impact in gold chemistry, as it introduced to the field the highly valued concept of gold carbene generation via alkyne oxidation. The proposed intermediacy of α-oxo gold carbenes in these reactions, however, has never been substantiated. Detailed experimental studies suggest that the involvement of such reactive intermediates in the formation of dihydrobenzothiepinones is highly unlikely. Instead, a [3,3]-sigmatropic rearrangement of the initial cyclization intermediate offers a reaction path that can readily explain the high reaction efficiency and the lack of sulfonium formation. With internal alkyne substrates, however, the generation of a gold carbene species becomes competitive with the [3,3]-sigmatropic rearrangement. This reactive intermediate, nevertheless, does not proceed to afford the Friedel-Crafts-type cyclization product. Extensive density functional theory studies support the mechanistic conclusion that the cyclized product is formed via an intramolecular [3,3]-sigmatropic rearrangement instead of the previously proposed Friedel-Crafts-type cyclization. With the new mechanistic insight, the product scope of this versatile formation of mid-sized sulfur-containing cycloalkenones has been expanded readily to various dihydrobenzothiocinones, a tetrahydrobenzocyclononenone, and even those without the entanglement of a fused benzene ring. Besides gold, Hg(OTf)2 can be an effective catalyst, thereby offering a cheap alternative for this intramolecular redox reaction.

  18. [3,3]-Sigmatropic Rearrangement vs. Carbene Formation in Gold-Catalyzed Transformations of Alkynyl Aryl Sulfoxides: Mechanistic Studies and Expanded Reaction Scope (United States)

    Lu, Biao; Li, Yuxue; Wang, Youliang; Aue, Donald H.; Luo, Yingdong; Zhang, Liming


    Gold-catalyzed intramolecular oxidation of terminal alkynes with an arenesulfinyl group as the tethered oxidant is a reaction in gold chemistry of high impact, as it introduced to the field the highly-valued concept of gold carbene generation via alkyne oxidation. The proposed intermediacy of α-oxo gold carbenes in these reactions, however, has never been substantiated. Detailed experimental studies suggest that the involvement of such reactive intermediates in the formation of dihydrobenzothiepinones is highly unlikely. Instead, a [3,3]-sigmatropic rearrangement of the initial cyclization intermediate offers a reaction path that can readily explain the high reaction efficiency and the lack of sulfonium formation. With internal alkyne substrates, however, the generation of a gold carbene species becomes competitive with the [3,3]-sigmatropic rearrangement. This reactive intermediate, nevertheless, does not proceed to afford the Friedel-Crafts type cyclization product. Extensive Density Functional Theory studies support the mechanistic conclusion that the cyclized product is formed via an intramolecular [3,3]-sigmatropic rearrangement instead of the previously proposed Friedel-Crafts type cyclization. With the new mechanistic insight, the product scope of this versatile formation of mid-sized sulfur-containing cycloalkenones has been expanded readily to various dihydrobenzothiocinones, a tetrahydrobenzocyclononenone, and even those without the entanglement of a fused benzene ring. Besides gold, Hg(OTf)2 can be an effective catalyst, thereby offering a cheap alternative for this intramolecular redox reaction. PMID:23731178

  19. Low-Valent Ate Complexes Formed in Cobalt-Catalyzed Cross-Coupling Reactions with 1,3-Dienes as Additives. (United States)

    Kreyenschmidt, Friedrich; Koszinowski, Konrad


    The combination of CoCl2 and 1,3-dienes is known to catalyze challenging alkyl-alkyl cross-coupling reactions between Grignard reagents and alkyl halides, but the mechanism of these valuable transformations remains speculative. Herein, electrospray-ionization mass spectrometry is used to identify and characterize the elusive intermediates of these and related reactions. The vast majority of detected species contain low-valent cobalt(I) centers and diene molecules. Charge tagging, deuterium labeling, and gas-phase fragmentation experiments elucidate the likely origin of these species and show that the diene not only binds to Co as a π ligand, but also undergoes migratory insertion reactions into Co-H and Co-R bonds. The resulting species have a strong tendency to form anionic cobalt(I) ate complexes, the superior nucleophilicity of which should render them highly reactive toward electrophilic substrates and, thus, presumably is the key to the high catalytic efficiency of the system under investigation. Upon the reaction of the in situ formed cobalt(I) ate complexes with organyl halides, only the final cross-coupling product could be detected, but no cobalt(III) species. This finding implies that this reaction step proceeds in a direct manner without any intermediate or, alternatively, that it involves an intermediate with a very short lifetime. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Concerted action of three distinct domains in the DNA cleaving-joining reaction catalyzed by relaxase (TraI) of conjugative plasmid RP4. (United States)

    Pansegrau, W; Schröder, W; Lanka, E


    The TraI protein of plasmid RP4 (IncP alpha) catalyzes a site- and strand-specific cleaving-joining reaction on form I or single-stranded DNA. Thus, TraI is one of the key components involved in the initiation and termination of horizontal DNA transfer by bacterial conjugation. Amino acid sequence comparison revealed three motifs in the TraI sequence conserved in relaxases from different origins. Site-directed mutagenesis of the traI structural gene and application of purified mutant TraI proteins for in vitro assays served to evaluate the functional importance of conserved amino acid residues. Two regions of TraI designated as motifs I and III are involved in catalyzing the cleaving-joining reaction. Motif I carries the tyrosine residue (Tyr-22), which covalently attaches TraI in a transesterification reaction to the 5' terminus of the cleaved DNA. Motif III contains one histidine residue (His-116) essential for relaxase activity and therefore proposed to activate the aromatic hydroxyl group of tyrosine 22 by proton abstraction. Exchange of a serine residue (Ser-74), located in motif II, against alanine prevents formation of stable relaxosomes but strongly enhances topoisomerase activity of the combination TraI/TraJ on form I oriT DNA. Motif II therefore might represent the DNA recognition domain of TraI. Our studies allowed us to establish a model of the interplay of three motifs located in the N-terminal region (amino acid positions 19-124) of TraI.

  1. Relaxase (TraI) of IncP alpha plasmid RP4 catalyzes a site-specific cleaving-joining reaction of single-stranded DNA. (United States)

    Pansegrau, W; Schröder, W; Lanka, E


    Conjugative DNA transfer of the self-transmissible broad-host-range plasmid RP4 is initiated by strand- and site-specific cleavage at the nick site (nic) of the transfer origin (oriT). Cleavage results in covalent attachment of the plasmid-encoded relaxase (TraI) to the 5'-terminal 2'-deoxycytidine residue at nic. We demonstrate that Tyr22 is the center of the catalytic site of TraI, mediating cleavage via formation of a phosphodiester between the DNA 5' phosphoryl and the aromatic hydroxyl group. The specificity of cleavage seen with form I oriT DNA was verified with short oligodeoxy-ribonucleotides embracing the nick region. The reaction requires TraI and Mg2+ but is independent of the relaxosome component TraJ. Cleavage produces one oligonucleotide fragment with a free 3' hydroxyl, the other part forms a covalent TraI-oligonucleotide adduct. Like nicking of form I oriT DNA, TraI-catalyzed oligonucleotide cleavage reaches an equilibrium when about 30% of the input TraI exists as a covalent protein-DNA complex. In the presence of two differently sized oligonucleotides, defined hybrid oligonucleotides are produced, demonstrating that TraI catalyzes recombination of two single strands at nic. This finding shows that TraI possesses cleaving-joining activity resembling that of a type I topoisomerase. Reactions are dependent on the sequence of the 3'-terminal 6 nucleotides adjacent to nic. Only certain base changes in a few positions are tolerated, whereas the sequence of the 5' terminal nucleotides apparently is irrelevant for recognition by TraI. The reactions described here further support the hypothesis that DNA transfer via conjugation involves a rolling circle-like mechanism which generates the immigrant single strand while DNA-bound TraI protein scans for the occurrence of a second cleavage site at the donor-recipient interface.

  2. Enantioselective construction of spirocyclic oxindoles via Tandem michael/Michael reactions catalyzed by multifunctional quaternary phosphonium salt

    National Research Council Canada - National Science Library

    Hongyu Wang; Yongjia Shang; Dongdong Cao; Jiaxing Zhang; Gang Zhao; Changwu Zheng


    The enantioselective construction of five-membered spirocyclic oxindoles via a double Michael cascade reaction is described by using dipeptide-based multifunctional quaternary phosphonium salt catalysts...

  3. Direct Carboxylation of C(sp3-H and C(sp2-H Bonds with CO2 by Transition-Metal-Catalyzed and Base-Mediated Reactions

    Directory of Open Access Journals (Sweden)

    Immacolata Tommasi


    Full Text Available This review focuses on recent advances in the field of direct carboxylation reactions of C(sp3-H and C(sp2-H bonds using CO2 encompassing both transition-metal-catalysis and base-mediated approach. The review is not intended to be comprehensive, but aims to analyze representative examples from the literature, including transition-metal catalyzed carboxylation of benzylic and allylic C(sp3-H functionalities using CO2 which is at a “nascent stage”. Examples of light-driven carboxylation reactions of unactivated C(sp3-H bonds are also considered. Concerning C(sp3-H and C(sp2-H deprotonation reactions mediated by bases with subsequent carboxylation of the carbon nucleophile, few examples of catalytic processes are reported in the literature. In spite of this, several examples of base-promoted reactions integrating “base recycling” or “base regeneration (through electrosynthesis” steps have been reported. Representative examples of synthetically efficient, base-promoted processes are included in the review.

  4. Substrates emulsification process to improve lipase-catalyzed sardine oil glycerolysis in different systems. Evaluation of lipid oxidation of the reaction products. (United States)

    Solaesa, Ángela García; Sanz, María Teresa; Melgosa, Rodrigo; Beltrán, Sagrario


    Mono- and diacylglycerols rich in omega-3 have a great interest due to their good bioavailability and oxidation stability compared with other kind of omega-3 concentrates. The main drawback in mono- and diacylglycerols production by glycerolysis is the immiscibility of the substrates, oil and glycerol. To improve mass transfer rates, avoiding the use of organic solvents, emulsification of both reactants as reverse micelles (glycerol-in-oil) was carried out previous to lipase-catalyzed sardine oil glycerolysis. Substrate emulsification yielded higher reaction rates compared to kinetics with no previous emulsification, but still lower than in organic solvents. To avoid the use of organic solvent, SC-CO 2 was used as reaction medium but no kinetic advantages were demonstrated in the pressure range from 15 to 25 MPa. By increasing temperature, from 40 to 90°C, reaction rates increased both in a solvent-free system and in SC-CO 2 medium. It was also found that an increase in temperature does not lead to an increase in the final oxidation status of the reaction products. This behavior was due to the adsorption capacity of the Lipozyme 435 support, giving lower oxidation status at the highest temperature, 80-90°C. Copyright © 2017 Elsevier Ltd. All rights reserved.

  5. Rhodium-catalyzed [5 + 2 + 1] cycloaddition of ene-vinylcyclopropanes and CO: reaction design, development, application in natural product synthesis, and inspiration for developing new reactions for synthesis of eight-membered carbocycles. (United States)

    Wang, Yi; Yu, Zhi-Xiang


    Practical syntheses of natural products and their analogues with eight-membered carbocyclic skeletons are important for medicinal and biological investigations. However, methods and strategies to construct the eight-membered carbocycles are limited. Therefore, developing new methods to synthesize the eight-membered carbocycles is highly desired. In this Account, we describe our development of three rhodium-catalyzed cycloadditions for the construction of the eight-membered carbocycles, which have great potential in addressing the challenges in the synthesis of medium-sized ring systems. The first reaction described in this Account is our computationally designed rhodium-catalyzed two-component [5 + 2 + 1] cycloaddition of ene-vinylcyclopropanes (ene-VCPs) and CO for the diastereoselective construction of bi- and tricyclic cyclooctenones. The design of this reaction is based on the hypothesis that the C(sp(3))-C(sp(3)) reductive elimination of the eight-membered rhodacycle intermediate generated from the rhodium-catalyzed cyclopropane cleavage and alkene insertion, giving Wender's [5 + 2] cycloadduct, is not easy. Under CO atmosphere, CO insertion may occur rapidly, converting the eight-membered rhodacycle into a nine-membered rhodacycle, which then undergoes an easy C(sp(2))-C(sp(3)) reductive elimination process and furnishes the [5 + 2 + 1] product. This hypothesis was supported by our preliminary DFT studies and also served as inspiration for the development of two [7 + 1] cycloadditions: the [7 + 1] cycloaddition of buta-1,3-dienylcyclopropanes (BDCPs) and CO for the construction of cyclooctadienones, and the benzo/[7 + 1] cycloaddition of cyclopropyl-benzocyclobutenes (CP-BCBs) and CO to synthesize the benzocyclooctenones. The efficiency of these rhodium-catalyzed cycloadditions can be revealed by the application in natural product synthesis. Two eight-membered ring-containing natural products, (±)-asterisca-3(15),6-diene and (+)-asteriscanolide, have been

  6. Bismuth(III) trifluoromethanesulfonate catalyzed ring opening reaction of mono epoxy oleochemicals to form keto and diketo derivatives (United States)

    Using a catalytic system, methyl oleate is transformed into long chain keto and diketo derivatives via an epoxide route. Methyl 9(10)-oxooctadecanoate and methyl 9,10-dioxooctadecanoate were made by a ring opening reaction of epoxidized methyl oleate using bismuth triflate catalyst. Lower reaction t...

  7. Palladium on Carbon-Catalyzed Suzuki-Miyaura Coupling Reaction Using an Efficient and Continuous Flow System

    Directory of Open Access Journals (Sweden)

    Tomohiro Hattori


    Full Text Available The continuous flow Suzuki-Miyaura reaction between various haloarenes and arylboronic acids was successfully achieved within only ca. 20 s during the single-pass through a cartridge filled with palladium on carbon (Pd/C. No palladium leaching was observed in the collected reaction solution by atomic absorption spectrometry (detection limit: 1 ppm.

  8. Hexacationic Dendriphos ligands in the Pd-catalyzed Suzuki-Miyaura cross-coupling reaction: scope and mechanistic studies

    NARCIS (Netherlands)

    Snelders, D.J.M.; van Koten, G.; Klein Gebbink, R.J.M.


    The combination of Pd2dba3·CHCl3and hexacationic triarylphosphine-based Dendriphos ligands (1-3) leads to a highly active catalytic system in the Suzuki-Miyaura cross-coupling reaction. Under relatively mild reaction conditions, nonactivated aryl bromides and activated aryl chlorides can be coupled

  9. A novel 4-aminoantipyrine-Pd(II complex catalyzes Suzuki–Miyaura cross-coupling reactions of aryl halides

    Directory of Open Access Journals (Sweden)

    Claudia A. Contreras-Celedón


    Full Text Available A simple and efficient catalytic system based on a Pd complex of 4-aminoantipyrine, 4-AAP–Pd(II, was found to be highly active for Suzuki–Miyaura cross-coupling of aryl iodides and bromides with phenylboronic acids under mild reaction conditions. Good to excellent product yields from the cross-coupling reaction can be achieved when the reaction is carried out in ethanol, in the open air, using low loading of 4-AAP–Pd(II as a precatalyst, and in the presence of aqueous K2CO3 as the base. A variety of functional groups are tolerated.

  10. Cu (II-Catalyzed Asymmetric Henry Reaction with a Novel C1-Symmetric Aminopinane-Derived Ligand

    Directory of Open Access Journals (Sweden)

    Liudmila Filippova


    Full Text Available A novel C1-symmetric dinitrogen ligand was synthesized in high yield from commercially available (1R,2R,3R,5S-(−-isopinocampheylamine and 1-methyl-2-imidazolecarboxaldehyde. In combination with Cu(OAc2H2O, this new ligand promote the reaction between nitromethane and aliphatic aldehydes with high yields (up to 97% and moderate enantioselectivities (up to 67% ee. The reactions with benzaldehyde required prolonged reaction time that resulted in diminished yields, but accompanied with ee-values in the 55%–76% range.

  11. Visualization of enzyme-catalyzed reactions using pH indicators: rapid screening of hydrolase libraries and estimation of the enantioselectivity. (United States)

    Morís-Varas, F; Shah, A; Aikens, J; Nadkarni, N P; Rozzell, J D; Demirjian, D C


    The use of pH indicators to monitor hydrolase-catalyzed reactions is described. The formation of acid following an enzyme-mediated hydrolysis causes a drop in the pH that can be visualized by a change in the color of the indicator-containing solution. The best indicators are those showing a color transition within the operational pH range of the hydrolases, like bromothymol blue and phenol red. The enantioselectivity of lipases and esterases can be estimated using single isomers under the same conditions and comparing the color turnover for each one. The method has been tested to quickly evaluate the enantioselectivity of a lipase towards a set of ester substrates and applied to the hierarchical screening of a library of thermophilic esterases.

  12. Synthesis of Bioactive 2-(Arylaminothiazolo[5,4-f]-quinazolin-9-ones via the Hügershoff Reaction or Cu- Catalyzed Intramolecular C-S Bond Formation

    Directory of Open Access Journals (Sweden)

    Damien Hédou


    Full Text Available A library of thirty eight novel thiazolo[5,4-f]quinazolin-9(8H-one derivatives (series 8, 10, 14 and 17 was prepared via the Hügershoff reaction and a Cu catalyzed intramolecular C-S bond formation, helped by microwave-assisted technology when required. The efficient multistep synthesis of the key 6-amino-3-cyclopropylquinazolin-4(3H-one (3 has been reinvestigated and performed on a multigram scale from the starting 5-nitroanthranilic acid. The inhibitory potency of the final products was evaluated against five kinases involved in Alzheimer’s disease and showed that some molecules of the 17 series described in this paper are particularly promising for the development of novel multi-target inhibitors of kinases.

  13. A computational study of base-catalyzed reactions of cyclic 1,2-diones: cyclobutane-1,2-dione

    Directory of Open Access Journals (Sweden)

    Nargis Sultana


    Full Text Available The reaction of cyclobutane-1,2-dione with hydroxide was studied by a variety of ab initio (MP2, SCS-MP2, CCSD(T, CEPA/1 and density functional (M06-2X methods. Three possible reaction paths of the initially formed tetrahedral adduct leading to either 1-hydroxycyclopropane-1-carboxylate (benzilic acid type rearrangement, path A, α-oxobutanoate (path B or γ-oxobutanoate (path C were considered. Although the latter two products show similar or even more negative Gibbs free energies of reaction than calculated for the benzilic acid type rearrangement, the Gibbs free energies of activation are substantially higher. According to the calculations, the only feasible reaction appears to be the formation of 1-hydroxycyclopropane-1-carboxylate, which is corroborated by previous experimental observations.

  14. Palladium-Catalyzed Heck Coupling Reaction of Aryl Bromides in Aqueous Media Using Tetrahydropyrimidinium Salts as Carbene Ligands

    Directory of Open Access Journals (Sweden)

    İsmail Özdemir


    Full Text Available An efficient and stereoselective catalytic system for the Heck cross coupling reaction using novel 1,3-dialkyl-3,4,5,6-tetrahydropyrimidinium salts (1, LHX and Pd(OAc2 loading has been reported. The palladium complexes derived from the salts 1a-f prepared in situ exhibit good catalytic activity in the Heck coupling reaction of aryl bromides under mild conditions.

  15. Suzuki Coupling Reactions Catalyzed by PdO Dispersed on Dealuminated Y Zeolite in Air under Ambient Conditions. (United States)

    Okumura, Kazu; Mushiake, Takumi; Matsui, Yu; Ishii, Akira


    Suzuki coupling reactions are performed using PdO loaded on dealuminated Y (USY) zeolite. The reaction between bromobenzene and phenylboronic acid is complete in 15 min at room temperature in air, with a turnover number of 1300. The reaction can be repeated at least five times by using 1 wt % Pd. Inductively coupled plasma analysis does not reveal the dissolution of Pd from products, even if the reaction is repeated up to four times. Pd K-edge extended X-ray absorption fine structure analysis reveals the presence of molecular-like PdO and a mixture of Pd(0) -PdO before and after the reaction, respectively. This is probably because Pd stabilized by Al sites is present at the II sites of the Y-type zeolite, as estimated using first-principles calculations. Conversely, Pd species change to PdO clusters after repeated reactions in air using the thermally treated sample. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Facile one-pot synthesis of 1-amido alkyl-2-naphthols by RuCl{sub 2}(PPh{sub 3}){sub 3}-catalyzed multi-component reactions

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, Xiaoyan; Lee, Yong Rok [Yeungnam Univ., Gyeongsan (Korea, Republic of); Kim, Sung Hong [Korea Basic Science Institute, Daegu (Korea, Republic of)


    We have developed an efficient and general synthesis of 1-amidoalkyl-2-naphthols by RuCl{sub 2}(PPh{sub 3}){sub 3}-catalyzed one-pot multi-component reaction of 2-naphthol with aromatic aldehydes and amides. The advantages of these methodologies are easy handling, mild reaction conditions, and use of an effective and non-toxic catalyst. Molecules bearing 1,3-amino oxygenated functional groups have been reported to exhibit a variety of biological and pharmacological activities including nucleoside antibiotics and HIV protease inhibitors such as ritonavir and lipinavir. Importantly, 1-amidoalkyl-2-naphthols can be easily converted to biologically active 1-aminomethyl-2-naphthols by amide hydrolysis. These compounds also exhibit potent antihypertensive, adrenoceptor-blocking, and Ca{sup +2} channel-blocking activities. Because of the importance of these compounds, numerous methods for the synthesis of 1-amidoalkyl-2-naphthols have been described. The reported methods mainly include one-pot three-component reactions of 2-naphthol, aromatic aldehydes, and amides.

  17. Laccase-catalyzed reactions of 17β-estradiol in the presence of humic acid: Resolved by high-resolution mass spectrometry in combination with (13)C labeling. (United States)

    Sun, Kai; Luo, Qi; Gao, Yanzheng; Huang, Qingguo


    The widespread presence of estrogens in natural waters poses potential threats to the aquatic organisms and human health. It is known that estrogens undergo enzyme-catalyzed oxidative coupling (ECOC) reactions, which may impact their environmental fate and can be used in wastewater treatment to remove estrogens, but little information is available on how natural organic matter (NOM) may influence 17β-estradiol (E2) transformation in ECOC processes. A series of experiments were conducted to examine the transformation of E2 in aqueous solution containing humic acid (HA) as model NOM by laccase-mediated ECOC reactions. The impact of HA on the reaction behaviors and product distribution is systematically characterized. The presence of HA inhibited the extent of E2 self-coupling in laccase-mediated systems, while promoted cross-coupling between E2 and HA. Reconfiguration of humic molecules was also observed and characterized by changes in absorbance at 275 nm and the ratios between A250 nm/A365 nm. In particular, experiments were conducted with un-labeled E2 mixed with (13)C3-labeled E2 at a set ratio, with the products probed using high-resolution mass spectrometry (HRMS). The high m/z accuracy of HRMS enabled the use of isotope ratio as a tracer to identify possible cross-coupling products between E2 and HA. Such a method combining HRMS and isotope labeling provides a novel means for identification of products in a reaction system involving NOM or other complex matrices. These findings provide a basis for optimization of ECOC reactions for estrogen removal, and also help to understand the environmental transformation of estrogens. Copyright © 2015 Elsevier Ltd. All rights reserved.

  18. Kinetic data for the transmetalation/reductive elimination in palladium-catalyzed Suzuki-Miyaura reactions: unexpected triple role of hydroxide ions used as base. (United States)

    Amatore, Christian; Jutand, Anny; Le Duc, Gaëtan


    The mechanism of the reaction of trans-[ArPdX(PPh(3))(2)] (Ar=p-Z-C(6)H(4); Z=CN, F, H; X=I, Br, Cl) with Ar'B(OH)(2) (Ar'=p-Z'-C(6)H(4); Z'=CN, H, OMe) has been established in DMF in the presence of the base OH(-) in the context of real palladium-catalyzed Suzuki-Miyaura reactions. The formation of the cross-coupling product ArAr' and [Pd(0)(PPh(3))(3)] has been followed through the application of electrochemical techniques. Kinetic data have been obtained for the first time, with determination of the observed rate constant, k(obs), of the overall reaction. trans-[ArPdX(PPh(3))(2)] is not reactive in the absence of the base. The base OH(-) plays three roles. It favors the reaction: 1) by formation of trans-[ArPd(OH)(PPh(3))(2)], a key complex which, in contrast to trans-[ArPdX(PPh(3))(2)], reacts with Ar'B(OH)(2) (rate-determining transmetalation), and 2) by unexpected promotion of the reductive elimination from the intermediate trans-[ArPdAr'(PPh(3))(2)], which generates ArAr' and a Pd(0) species. Conversely, the base OH(-) disfavors the reaction by formation of the unreactive anionic Ar'B(OH)(3)(-). As a consequence of these antagonistic effects of OH(-), the overall reactivity is controlled by the concentration of OH(-) and passes through a maximum as the concentration of OH(-) is increased. Therefore, the base favors the rate-determining transmetalation and unexpectedly also the reductive elimination. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Hemin- and myoglobin-catalyzed reaction of 1-palmitoyl-2-linoleoyl-3-sn-phosphatidylcholine 13-hydroperoxide with γ-tocopherol in micelles and liposomes. (United States)

    Yamauchi, Ryo; Kinoshita, Tomomi; Hasegawa, Yoshinori; Iwamoto, Satoshi


    The secondary process of lipid peroxidation proceeds by the free radical reaction to produce some toxic aldehydes. Since γ-tocopherol (γ-TH), one of the major forms of vitamin E in some vegetable oils, acts as a free radical scavenger, γ-TH may suppress the formation of such aldehydes. This study reports the effect and reaction products of γ-TH on the hemin- or myoglobin-catalyzed decomposition of 1-palmitoyl-2-linoleoyl-3-sn-phosphatidylcholine 13-hydroperoxide (PLPC-OOH) in micelles and liposomes. γ-TH and PLPC-OOH in micelles were reacted in the presence of hemin, and the reaction products were characterized as 1-palmitoyl-2-[(8a-dioxy-γ-tocopherone)-12,13-epoxyoctadecenoyl]-3-sn-phosphatidylcholines (γT-OO-epoxyPLPC), 1-palmitoyl-2-[(γ-tocopheroxy)-12,13-epoxyoctadecenoyl]-3-sn-phosphatidylcholines (γT-epoxyPLPC), and the adducts of γ-TH dimer with PLPC-OOH derived epoxyperoxyl and epoxyalkyl radicals (γTD-OO-epoxyPLPC and γTD-epoxyPLPC). The hemin- and myoglobin-catalyzed decomposition of PLPC-OOH in micelles produced hexanal and 4-hydroxy-2-nonenal as the major aldehydic products. γ-TH suppressed the formation of these aldehydes as the same level as α-TH did, and γ-tocopherylquinone, tocored, γ-TH dimers, and the addition products (γT-OO-epoxyPLPC, γT-epoxyPLPC, γTD-OO-epoxyPLPC, and γTD-epoxyPLPC) were formed during the reaction. In liposomes, hexanal was detected as the major aldehyde and its suppression by γ-TH was less effective than that by α-TH. The results indicate that γ-TH may suppress the formation of aldehydes by trapping the epoxyperoxyl and epoxyalkyl radicals derived from PLPC-OOH although its ability is weak in liposomal systems. Copyright © 2017 Elsevier B.V. All rights reserved.

  20. A Multistep Organocatalysis Experiment for the Undergraduate Organic Laboratory: An Enantioselective Aldol Reaction Catalyzed by Methyl Prolinamide (United States)

    Wade, Edmir O.; Walsh, Kenneth E.


    In recent years, there has been an explosion of research concerning the area of organocatalysis. A multistep capstone laboratory project that combines traditional reactions frequently found in organic laboratory curriculums with this new field of research is described. In this experiment, the students synthesize a prolinamide-based organocatalyst…

  1. Study of Fe2O3, CuO, ZnO catalyzed efficient Hantzsch reaction under different conditions

    Directory of Open Access Journals (Sweden)

    Mohammad Reza Shushizadeh


    Full Text Available 1,4-dihydropyridine derivatives one-pot synthesis under different condition was described. CuO nanoparticle as a catalyst in microwave irradiation (100w gives product with excellent yields (≥87% and short reaction time. No significant difference was observed between the obtained yield by using ZnO and Fe2O3.

  2. N-Heterocyclic carbene-palladium(II)-1-methylimidazole complex catalyzed Mizoroki-Heck reaction of aryl chlorides with styrenes

    National Research Council Canada - National Science Library

    Gao, Ting-Ting; Jin, Ai-Ping; Shao, Li-Xiong


    A well-defined N-heterocyclic carbene-palladium(II)-1-methylimidazole [NHC-Pd(II)-Im] complex 1 was found to be an effective catalyst for the Mizoroki-Heck reaction of a variety of aryl chlorides with styrenes...

  3. Modular synthesis of optically active lactones by Ru-catalyzed asymmetric allylic carboxylation and ring-closing metathesis reaction. (United States)

    Takii, Koichiro; Kanbayashi, Naoya; Onitsuka, Kiyotaka


    A new synthetic route to optically active unsaturated γ- and δ-lactones has been demonstrated via asymmetric allylic carboxylation with a planar-chiral Cp'Ru catalyst and ring-closing metathesis reaction with a Grubbs II catalyst, and successfully applied to the enantioselective synthesis of (R)-(-)-massoialactone. This journal is © The Royal Society of Chemistry 2012

  4. Ab initio calculations on 2,6-dimethylphenol and 4-(2,6-dimethylphenoxy)-2,6-dimethylphenol. Evidence of an important role for the phenoxonium cation in the copper-catalyzed oxidative phenol coupling reaction

    NARCIS (Netherlands)

    Baesjou, PJ; Driessen, WL; Challa, G; Reedijk, J


    Ab initio unrestricted Hartree-Fock calculations with a 6-31G* basis set were performed on 2, 6-dimethylphenol (DMP or monomer) and 4-(2, 6-dimethylphenoxy)-2, 6-dimethylphenol (dimer) to gain more insight into the mechanism of the copper-catalyzed oxidative phenol coupling reaction. Atomic charges

  5. Lipase-catalyzed glycerolysis of fats and oils in ionic liquids: a further study on the reaction system

    DEFF Research Database (Denmark)

    Guo, Zheng; Xu, Xuebing


    ) equation, and the viscosity of the mixture is strongly agitation-dependent. A comparable diffusion time constant of the oil molecule in the IL to that of the reaction shows that the glycerolysis in the IL is controlled both diffusionally and kinetically, as experimentally verified by agitation effect...... and enzyme loading study. Interestingly, increasing water activity resulted in a decreasing initial reaction rate and a prolonged induction period, which possibly resulted from an elevated solvation barrier and the phase separation at higher water content. Studies on thermodynamics of glycerolysis show...... that there is a bigger energy barrier for the IL system, about 1.5 times that of the solvent-free or 3 times that of the tert-butyl alcohol system. Kinetic studies also show that IL system has the biggest Vmax and Km among the three tested systems, indicating, respectively, its high productivity, and low substrate...

  6. Condensed tannins: The formation of a diarylpropanol-catechinic acid dimer from base-catalyzed reactions of (+)-catechin (United States)

    Seiji Ohara; Richard W. Hemingway


    Reaction of (+ )-catechin at pH 12 and 40 DC results in the stereoselective (if not stereospecific) formation of an enolic form of 1-[6-(3',4'-dihydroxyphenyl)-7-hydroxybicyclo[3.3.1]nonane-2,4,9-trione-3-yl]-1-(3,4-dihyroxyphenyl)-3-(2,-4,6-trihydroxyphenyl)-propan-2-ol. The n.m.r. chemical shift assignments determined by a variety of two-dimensional...

  7. Gold-catalyzed reaction of oxabicyclic alkenes with electron-deficient terminal alkynes to produce acrylate derivatives

    Directory of Open Access Journals (Sweden)

    Yin-wei Sun


    Full Text Available Oxabicyclic alkenes can react with electron-deficient terminal alkynes in the presence of a gold catalyst under mild conditions, affording the corresponding addition products in moderate yields. When using alkynyl esters as substrates, the (Z-acrylate derivatives are obtained. Using but-3-yn-2-one (ethynyl ketone as a substrate, the corresponding addition product is obtained with (E-configuration. The proposed mechanism of these reactions is also discussed.

  8. Ionic liquids as recyclable and separable reaction media in Rh-catalyzed decarbonylation of aromatic and aliphatic aldehydes

    DEFF Research Database (Denmark)

    Malcho, Phillip; Garcia-Suarez, Eduardo J.; Riisager, Anders


    Ionic liquids (ILs) have been applied as recyclable reaction media in the decarbonylation of aldehydes in the presence of a rhodium-phosphine complex catalyst. The performance of several new catalytic systems based on imidazolium-based ILs and [Rh(dppp)2]Cl (dppp: 1,3-diphenylphosphinopropane) were...... as a biphasic system with the product allowing recovery and reuse of the employed catalyst....

  9. N-Heterocyclic carbene–palladium(II-1-methylimidazole complex catalyzed Mizoroki–Heck reaction of aryl chlorides with styrenes

    Directory of Open Access Journals (Sweden)

    Ting-Ting Gao


    Full Text Available A well-defined N-heterocyclic carbene–palladium(II-1-methylimidazole [NHC-Pd(II-Im] complex 1 was found to be an effective catalyst for the Mizoroki–Heck reaction of a variety of aryl chlorides with styrenes. Both activated and deactivated aryl chlorides work well to give the corresponding coupling products in good to excellent yields by using tetrabutylammonium bromide (TBAB as the ionic liquid.

  10. Influence of the reaction conditions on the enzyme catalyzed transesterification of castor oil: A possible step in biodiesel production. (United States)

    Andrade, Thalles A; Errico, Massimiliano; Christensen, Knud V


    The identification of the influence of the reaction parameters is of paramount importance when defining a process design. In this work, non-edible castor oil was reacted with methanol to produce a possible component for biodiesel blends, using liquid enzymes as the catalyst. Temperature, alcohol-to-oil molar ratio, enzyme and added water contents were the reaction parameters evaluated in the transesterification reactions. The optimal conditions, giving the optimal final FAME yield and FFA content in the methyl ester-phase was identified. At 35°C, 6.0 methanol-to-oil molar ratio, 5wt% of enzyme and 5wt% of water contents, 94% of FAME yield and 6.1% of FFA in the final composition were obtained. The investigation was completed with the analysis of the component profiles, showing that at least 8h are necessary to reach a satisfactory FAME yield together with a minor FFA content. Copyright © 2017 Elsevier Ltd. All rights reserved.

  11. Borate-catalyzed reactions of hydrogen peroxide: kinetics and mechanism of the oxidation of organic sulfides by peroxoborates. (United States)

    Davies, D Martin; Deary, Michael E; Quill, Kieran; Smith, Robert A


    The kinetics of the oxidation of substituted phenyl methyl sulfides by hydrogen peroxide in borate/boric acid buffers were investigated as a function of pH, total peroxide concentration, and total boron concentration. Second-order rate constants at 25 degrees C for the reaction of methyl 4-nitrophenyl sulfide and H(2)O(2), monoperoxoborate, HOOB(OH)(3) (-), or diperoxoborate, (HOO)(2)B(OH)(2) (-), are 8.29 x 10(-5), 1.51 x 10(-2) and 1.06 x 10(-2) M(-1) s(-1), respectively. Peroxoboric acid, HOOB(OH)(2), is unreactive. The Hammett rho values for the reactions of a range of substituted phenyl methyl sulfides and hydrogen peroxide, monoperoxoborate or diperoxoborate are -1.50 +/- 0.1, -0.65 +/- 0.07 and -0.48 (two points only), respectively. The rho values for the peroxoborates are of significantly lower magnitude than expected from their reactivity compared to other peroxides. Nevertheless the negative rho values indicate positive charge development on the sulfur atom in the transition state consistent with nucleophilic attack by the organic sulfides on the peroxoborates as with the other peroxides. The kinetic parameters, including the lack of reactivity of peroxoboric acid, are discussed in terms of the differences in the transition state of reactions involving peroxoboron species with respect to those of other peroxides.

  12. Studies of Heterogeneously Catalyzed Liquid-Phase Alcohol Oxidation on Platinum bySum-frequency Generation Vibrational Spectroscopy and Reaction Rate Measurements

    Energy Technology Data Exchange (ETDEWEB)

    Thompson, Christopher [Univ. of California, Berkeley, CA (United States)


    Compared to many branches of chemistry, the molecular level study of catalytically active surfaces is young. Only with the invention of ultrahigh vacuum technology in the past half century has it been possible to carry out experiments that yield useful molecular information about the reactive occurrences at a surface. The reason is two-fold: low pressure is necessary to keep a surface clean for an amount of time long enough to perform an experiment, and most atomic scale techniques that are surface speci c (x-ray photoelectron spectroscopy, electron energy loss spectroscopy, Auger electron spectroscopy, etc.) cannot be used at ambient pressures, because electrons, which act as chemical probes in these techniques, are easily scattered by molecules. Sum-frequency generation (SFG) vibrational spectroscopy is one technique that can provide molecular level information from the surface without the necessity for high vacuum. Since the advent of SFG as a surface spectroscopic tool it has proved its worth in the studies of surface catalyzed reactions in the gas phase, with numerous reactions in the gas phase having been investigated on a multitude of surfaces. However, in situ SFG characterization of catalysis at the solid-liquid interface has yet to be thoroughly pursued despite the broad interest in the use of heterogeneous catalysts in the liquid phase as replacements for homogeneous counterparts. This work describes an attempt to move in that direction, applying SFG to study the solid-liquid interface under conditions of catalytic alcohol oxidation on platinum.

  13. Loop L1 governs the DNA-binding specificity and order for RecA-catalyzed reactions in homologous recombination and DNA repair (United States)

    Shinohara, Takeshi; Ikawa, Shukuko; Iwasaki, Wakana; Hiraki, Toshiki; Hikima, Takaaki; Mikawa, Tsutomu; Arai, Naoto; Kamiya, Nobuo; Shibata, Takehiko


    In all organisms, RecA-family recombinases catalyze homologous joint formation in homologous genetic recombination, which is essential for genome stability and diversification. In homologous joint formation, ATP-bound RecA/Rad51-recombinases first bind single-stranded DNA at its primary site and then interact with double-stranded DNA at another site. The underlying reason and the regulatory mechanism for this conserved binding order remain unknown. A comparison of the loop L1 structures in a DNA-free RecA crystal that we originally determined and in the reported DNA-bound active RecA crystals suggested that the aspartate at position 161 in loop L1 in DNA-free RecA prevented double-stranded, but not single-stranded, DNA-binding to the primary site. This was confirmed by the effects of the Ala-replacement of Asp-161 (D161A), analyzed directly by gel-mobility shift assays and indirectly by DNA-dependent ATPase activity and SOS repressor cleavage. When RecA/Rad51-recombinases interact with double-stranded DNA before single-stranded DNA, homologous joint-formation is suppressed, likely by forming a dead-end product. We found that the D161A-replacement reduced this suppression, probably by allowing double-stranded DNA to bind preferentially and reversibly to the primary site. Thus, Asp-161 in the flexible loop L1 of wild-type RecA determines the preference for single-stranded DNA-binding to the primary site and regulates the DNA-binding order in RecA-catalyzed recombinase reactions. PMID:25561575

  14. Delineating pMDI model reactions with loblolly pine via solution-state NMR spectroscopy. Part 1, Catalyzed reactions with wood models and wood polymers (United States)

    Daniel J. Yelle; John Ralph; Charles R. Frihart


    To better understand adhesive interactions with wood, reactions between model compounds of wood and a model compound of polymeric methylene diphenyl diisocyanate (pMDI) were characterized by solution-state NMR spectroscopy. For comparison, finely ground loblolly pine sapwood, milled-wood lignin and holocellulose from the same wood were isolated and derivatized with...

  15. A Rh(II)-catalyzed multicomponent reaction by trapping an α-amino enol intermediate in a traditional two-component reaction pathway (United States)

    Liu, Shunying; Yao, Wenfeng; Liu, Yuan; Wei, Qinghua; Chen, Jianghui; Wu, Xiang; Xia, Fei; Hu, Wenhao


    Multicomponent reactions (MCRs) represent an ideal organic synthesis tool for the rapid construction of complex molecules due to their step and atom economy. Compared to two-component reactions, the development of new MCRs has been greatly limited during the 170 years since the first MCR was reported. Theoretically, the trapping of an active intermediate generated from two components by a third component could change the traditional two-component reaction pathway, leading to the discovery of MCRs. We report an example of the trapping of α-imino enols generated in situ from 1-sulfonyl-1,2,3-triazoles via α-imino metal carbene species by vinylimine ions using C(2)-substituted indoles and paraformaldehyde as precursors in the presence of a rhodium(II) catalyst. The traditional enol-ketone transformation pathway was suspended by the trapping procedure and efficiently switched to an MCR pathway to produce α-amino-β-indole ketones in moderate to good yields. Unexpectedly, the resulting products and the theoretical density functional theory (DFT) calculation results indicated that the enolic carbon had a stronger nucleophilicity than the well-known traditional enamic carbon in the trapping process. The reaction mechanism was investigated using control experiments and detailed DFT calculations, and the synthetic application of the products was also illustrated. The developed strategy provides a mild and rapid access to α-amino-β-indole ketones and suggests a rationale for the discovery of MCRs by trapping an active intermediate with a third component in a traditional two-component reaction pathway. PMID:28345053

  16. Pd-Catalyzed Semmler-Wolff Reactions for the Conversion of Substituted Cyclohexenone Oximes to Primary Anilines (United States)

    Hong, Wan Pyo; Iosub, Andrei V.; Stahl, Shannon S.


    Homogeneous Pd catalysts have been identified for the conversion of cyclohexenone and tetralone O-pivaloyl oximes to the corresponding primary anilines and 1-aminonaphthalenes. This method is inspired by the Semmler-Wolff reaction, a classic method that exhibits limited synthetic utility owing to its forcing conditions, narrow scope and low product yields. The oxime N–O bond undergoes oxidative addition to Pd0(PCy3)2, and the product of this step has been characterized by X-ray crystallography and shown to undergo dehydrogenation to afford the aniline product. PMID:23987212

  17. Iridium-catalyzed C–H coupling reaction of heteroaromatic compounds with bis(pinacolato)diboron: regioselective synthesis of heteroarylboronates


    Takagi, Jun; Sato, Kazuaki; Hartwig, John F; Ishiyama, Tatsuo; Miyaura, Norio


    The C–H coupling of aromatic heterocycles with bis(pinacolato)diboron was carried out in octane at 80–100°C in the presence of a 1/2[IrCl(COD)]2-(4,4 -di-tert-butyl-2,2 -bipyridine) catalyst (3 mol%). The reactions of five-membered substrates such as thiophene, furan, pyrrole, and their benzo-fused derivatives exclusively produced 2-borylated products, whereas those of six-membered heterocycles including pyridine and quinoline selectively occurred at the 3-position. Regioselective sy...

  18. CYP-450 isoenzymes catalyze the generation of hazardous aromatic amines after reaction with the azo dye Sudan III. (United States)

    Zanoni, Thalita Boldrin; Lizier, Thiago M; Assis, Marilda das Dores; Zanoni, Maria Valnice B; de Oliveira, Danielle Palma


    This work describes the mutagenic response of Sudan III, an adulterant food dye, using Salmonella typhimurium assay and the generation of hazardous aromatic amines after different oxidation methods of this azo dye. For that, we used metabolic activation by S9, catalytic oxidation by ironporphyrin and electrochemistry oxidation in order to simulate endogenous oxidation conditions. The oxidation reactions promoted discoloration from 65% to 95% of Sudan III at 1 × 10(-4)molL(-1) and generation of 7.6 × 10(-7)molL(-1) to 0.31 × 10(-4)molL(-1) of aniline, o-anisidine, 2-methoxi-5-methylaniline, 4-aminobiphenyl, 4,4'-oxydianiline; 4,4'-diaminodiphenylmethane and 2,6-dimethylaniline. The results were confirmed by LC-MS-MS experiments. We also correlate the mutagenic effects of Sudan III using S. typhimurium with the strain TA1535 in the presence of exogenous metabolic activation (S9) with the metabolization products of this compound. Our findings clearly indicate that aromatic amines are formed due to oxidative reactions that can be promoted by hepatic cells, after the ingestion of Sudan III. Considering that, the use of azo compounds as food dyestuffs should be carefully controlled. Copyright © 2013 Elsevier Ltd. All rights reserved.

  19. TM0416, a Hyperthermophilic Promiscuous Nonphosphorylated Sugar Isomerase, Catalyzes Various C5 and C6 Epimerization Reactions. (United States)

    Shin, Sun-Mi; Cao, Thinh-Phat; Choi, Jin Myung; Kim, Seong-Bo; Lee, Sang-Jae; Lee, Sung Haeng; Lee, Dong-Woo


    There is currently little information on nonphosphorylated sugar epimerases, which are of potential interest for producing rare sugars. We found a gene (the TM0416 gene) encoding a putative d-tagatose-3-epimerase-related protein from the hyperthermophilic bacterium Thermotoga maritima We overexpressed the TM0416 gene in Escherichia coli and purified the resulting recombinant protein for detailed characterization. Amino acid sequence alignment and a structural similarity search revealed that TM0416 is a putative nonphosphorylated sugar epimerase. The recombinant enzyme exhibited maximal C-3 epimerization of l-ribulose to l-xylulose at ∼80°C and pH 7 in the presence of 1 mM Mn2+ In addition, this enzyme showed unusually high activity for the epimerization of d-tagatose to d-sorbose, with a conversion yield of 20% after 6 h at 80°C. Remarkably, the enzyme catalyzed the isomerization of d-erythrose or d-threose to d-erythrulose significantly, with conversion yields of 71% and 54.5%, respectively, after 6 h at 80°C at pH 7. To further investigate the substrate specificity of TM0416, we determined its crystal structures in complex with divalent metal ions and l-erythrulose at resolutions of 1.5 and 1.6 Å. Detailed inspection of the structural features and biochemical data clearly demonstrated that this metalloenzyme, with a freely accessible substrate-binding site and neighboring hydrophobic residues, exhibits different and promiscuous substrate preferences, compared with its mesophilic counterparts. Therefore, this study suggests that TM0416 can be functionally classified as a novel type of l-ribulose 3-epimerase (R3E) with d-erythrose isomerase activity.IMPORTANCE Rare sugars, which occur naturally in small amounts, have attracted considerable attention in the food and drug industries. However, there is little information on nonphosphorylated sugar epimerases, which might potentially be applied for the production of rare sugars. This study describes the

  20. Stereochemical course of hydrolytic reaction catalyzed by alpha-galactosidase from cold adaptable marine bacterium of genus Pseudoalteromonas (United States)

    Bakunina, Irina; Balabanova, Larissa; Golotin, Vasiliy; Slepchenko, Lyubov; Isakov, Vladimir; Rasskazov, Valeriy


    The recombinant α-galactosidase of the marine bacterium (α-PsGal) was synthesized with the use of the plasmid 40Gal, consisting of plasmid pET-40b (+) (Novagen) and the gene corresponding to the open reading frame of the mature α-galactosidase of marine bacterium Pseudoalteromonas sp. KMM 701, transformed into the E. coli Rosetta(DE3) cells. In order to understand the mechanism of action, the stereochemistry of hydrolysis of 4-nitrophenyl α-D-galactopyranoside (4-NPGP) by α-PsGal was measured by 1H NMR spectroscopy. The kinetics of formation of α- and β-anomer of galactose showed that α-anomer initially formed and accumulated, and then an appreciable amount of β-anomer appeared as a result of mutarotation. The data clearly show that the enzymatic hydrolysis of 4-NPGP proceeds with the retention of anomeric configuration, probably, due to a double displacement mechanism of reaction.

  1. Efficient transfer hydrogenation reaction Catalyzed by a dearomatized PN 3P ruthenium pincer complex under base-free Conditions

    KAUST Repository

    He, Lipeng


    A dearomatized complex [RuH(PN 3P)(CO)] (PN 3PN, N′-bis(di-tert-butylphosphino)-2,6-diaminopyridine) (3) was prepared by reaction of the aromatic complex [RuH(Cl)(PN 3P)(CO)] (2) with t-BuOK in THF. Further treatment of 3 with formic acid led to the formation of a rearomatized complex (4). These new complexes were fully characterized and the molecular structure of complex 4 was further confirmed by X-ray crystallography. In complex 4, a distorted square-pyramidal geometry around the ruthenium center was observed, with the CO ligand trans to the pyridinic nitrogen atom and the hydride located in the apical position. The dearomatized complex 3 displays efficient catalytic activity for hydrogen transfer of ketones in isopropanol. © 2011 Elsevier B.V. All rights reserved.

  2. Stereochemical course of hydrolytic reaction catalyzed by alpha-galactosidase from cold adaptable marine bacterium of genus Pseudoalteromonas

    Directory of Open Access Journals (Sweden)

    Irina Yu Bakunina


    Full Text Available The recombinant α-galactosidase of the marine bacterium (α-PsGal was synthesized with the use of the plasmid 40Gal, consisting of plasmid pET-40b (+ (Novagen and the gene corresponding to the open reading frame of the mature α-galactosidase of marine bacterium Pseudoalteromonas sp. KMM 701, transformed into the E. coli Rosetta(DE3 cells. In order to understand the mechanism of action, the stereochemistry of hydrolysis of 4-nitrophenyl α-D-galactopyranoside (4-NPGP by α-PsGal was measured by 1H NMR spectroscopy. The kinetics of formation of α- and β-anomer of galactose showed that α-anomer initially formed and accumulated, and then an appreciable amount of β-anomer appeared as a result of mutarotation. The data clearly show that the enzymatic hydrolysis of 4-NPGP proceeds with the retention of anomeric configuration, probably, due to a double displacement mechanism of reaction.

  3. Glycerolysis of sardine oil catalyzed by a water dependent lipase in different tert-alcohols as reaction medium

    Directory of Open Access Journals (Sweden)

    Solaesa, Á. G.


    Full Text Available The production of monoacylglycerol rich in polyunsaturated fatty acids (PUFA via enzymatic glycerolysis of sardine oil in a homogeneous system was evaluated. Reactions were conducted in two different tert-alcohols. Based on the phase equilibrium data, the amount of solvent added to create a homogeneous system has been calculated and optimized. The immobilized lipase used in this work was Lipozyme RM IM from Rhizomucor miehei, a water dependent lipase. The amount of water added as well as other reaction parameters were studied to evaluate the optimum conditions for monoacylglycerol obtencion. An initial reactant mole ratio glycerol to sardine oil 3:1, 12 wt% of water based on glycerol content and 10 wt% of lipase loading (based on weight of reactants, achieved a MAG yield of around 70%, with nearly 28 wt% PUFA, with low free fatty acid content (lower than 18 wt%.En este trabajo se ha estudiado la producción de monoacilglicéridos, ricos en ácidos grasos poliinsaturados (AGPI, mediante glicerolisis enzimática de aceite de sardina. La reacción se ha llevado a cabo en dos tert-alcoholes para conseguir de esta forma un medio homogéneo de reacción. La cantidad de disolvente añadida al medio de reacción se ha optimizado y calculado en base al equilibrio de fases de los componentes del sistema. La lipasa empleada como biocatalizador ha sido la enzima inmovilizada Lipozyme RM IM de Rhizomucor miehei, una lipasa dependiente de agua. Se ha estudiado el efecto de distintos parámetros cinéticos, así como de la cantidad de agua añadida al medio de reacción, en la producción de monoacilglicéridos. De los resultados obtenidos, se puede concluir que, para una relación molar inicial de reactantes glicerol:aceite de sardina de 3:1, un 12 % en peso de agua en base al glicerol y un 10 % en peso de lipasa, en base al peso de reactantes; se puede llegar a conseguir un rendimiento en monoacilglicéridos alrededor del 70 % en peso, con casi un 28 % en

  4. Kinetic analysis of PCNA clamp binding and release in the clamp loading reaction catalyzed by Saccharomyces cerevisiae replication factor C. (United States)

    Marzahn, Melissa R; Hayner, Jaclyn N; Meyer, Jennifer A; Bloom, Linda B


    DNA polymerases require a sliding clamp to achieve processive DNA synthesis. The toroidal clamps are loaded onto DNA by clamp loaders, members of the AAA+family of ATPases. These enzymes utilize the energy of ATP binding and hydrolysis to perform a variety of cellular functions. In this study, a clamp loader-clamp binding assay was developed to measure the rates of ATP-dependent clamp binding and ATP-hydrolysis-dependent clamp release for the Saccharomyces cerevisiae clamp loader (RFC) and clamp (PCNA). Pre-steady-state kinetics of PCNA binding showed that although ATP binding to RFC increases affinity for PCNA, ATP binding rates and ATP-dependent conformational changes in RFC are fast relative to PCNA binding rates. Interestingly, RFC binds PCNA faster than the Escherichia coli γ complex clamp loader binds the β-clamp. In the process of loading clamps on DNA, RFC maintains contact with PCNA while PCNA closes, as the observed rate of PCNA closing is faster than the rate of PCNA release, precluding the possibility of an open clamp dissociating from DNA. Rates of clamp closing and release are not dependent on the rate of the DNA binding step and are also slower than reported rates of ATP hydrolysis, showing that these rates reflect unique intramolecular reaction steps in the clamp loading pathway. Copyright © 2014 Elsevier B.V. All rights reserved.

  5. Organobase-catalyzed three-component reactions for the synthesis of 4H-2-aminopyrans, condensed pyrans and polysubstituted benzenes

    Directory of Open Access Journals (Sweden)

    Moustafa Sherief Moustafa


    Full Text Available Novel routes for the preparation of 2-amino-4H-pyran-3-carbonitrile 9, amino-arylbenzoic acid ester derivatives 13a,b, 2-aminotetrahydro-4H-chromene-3-carbonitrile 18, 3-amino-4-cyanotetrahydronaphthalene-2-carboxylic acid ester 26 and 4-amino-3,5-dicyanophthalic acid ester derivatives 37a–c were developed. The synthetic methods utilize one-pot reactions of acetylene carboxylic acid esters, α,β-unsaturated nitriles and/or active methylenenitriles in the presence of L-proline or DABCO. Plausible mechanisms are suggested for the formation of the products. Finally, these compounds were used for the efficient synthesis of 6-amino-5-cyanonicotinic acid ester derivatives 31a,b, ethyl 4-amino-5H-pyrano[2,3-d]pyrimidine-6-carboxylates 33a,b, 4-amino-6H-pyrrolo[3,4-g]quinazoline-9-carbonitrile 39, and 1,7-diamino-6-(N'-hydroxycarbamimidoyl-3-oxo-5-phenyl-3H-isoindole-4-carboxylate (40.

  6. Organobase-catalyzed three-component reactions for the synthesis of 4H-2-aminopyrans, condensed pyrans and polysubstituted benzenes. (United States)

    Moustafa, Moustafa Sherief; Al-Mousawi, Saleh Mohammed; Selim, Maghraby Ali; Mosallam, Ahmed Mohamed; Elnagdi, Mohamed Hilmy


    Novel routes for the preparation of 2-amino-4H-pyran-3-carbonitrile 9, amino-arylbenzoic acid ester derivatives 13a,b, 2-aminotetrahydro-4H-chromene-3-carbonitrile 18, 3-amino-4-cyanotetrahydronaphthalene-2-carboxylic acid ester 26 and 4-amino-3,5-dicyanophthalic acid ester derivatives 37a-c were developed. The synthetic methods utilize one-pot reactions of acetylene carboxylic acid esters, α,β-unsaturated nitriles and/or active methylenenitriles in the presence of L-proline or DABCO. Plausible mechanisms are suggested for the formation of the products. Finally, these compounds were used for the efficient synthesis of 6-amino-5-cyanonicotinic acid ester derivatives 31a,b, ethyl 4-amino-5H-pyrano[2,3-d]pyrimidine-6-carboxylates 33a,b, 4-amino-6H-pyrrolo[3,4-g]quinazoline-9-carbonitrile 39, and 1,7-diamino-6-(N'-hydroxycarbamimidoyl)-3-oxo-5-phenyl-3H-isoindole-4-carboxylate (40).

  7. The Molybdenum Active Site of Formate Dehydrogenase Is Capable of Catalyzing C-H Bond Cleavage and Oxygen Atom Transfer Reactions. (United States)

    Hartmann, Tobias; Schrapers, Peer; Utesch, Tillmann; Nimtz, Manfred; Rippers, Yvonne; Dau, Holger; Mroginski, Maria Andrea; Haumann, Michael; Leimkühler, Silke


    Formate dehydrogenases (FDHs) are capable of performing the reversible oxidation of formate and are enzymes of great interest for fuel cell applications and for the production of reduced carbon compounds as energy sources from CO2. Metal-containing FDHs in general contain a highly conserved active site, comprising a molybdenum (or tungsten) center coordinated by two molybdopterin guanine dinucleotide molecules, a sulfido and a (seleno-)cysteine ligand, in addition to a histidine and arginine residue in the second coordination sphere. So far, the role of these amino acids in catalysis has not been studied in detail, because of the lack of suitable expression systems and the lability or oxygen sensitivity of the enzymes. Here, the roles of these active site residues is revealed using the Mo-containing FDH from Rhodobacter capsulatus. Our results show that the cysteine ligand at the Mo ion is displaced by the formate substrate during the reaction, the arginine has a direct role in substrate binding and stabilization, and the histidine elevates the pKa of the active site cysteine. We further found that in addition to reversible formate oxidation, the enzyme is further capable of reducing nitrate to nitrite. We propose a mechanistic scheme that combines both functionalities and provides important insights into the distinct mechanisms of C-H bond cleavage and oxygen atom transfer catalyzed by formate dehydrogenase.

  8. Reaction Mechanisms of Metals with Hydrogen Sulfide and Thiols in Model Wine. Part 2: Iron- and Copper-Catalyzed Oxidation. (United States)

    Kreitman, Gal Y; Danilewicz, John C; Jeffery, David W; Elias, Ryan J


    Sulfidic off-odors arising during wine production are frequently removed by Cu(II) fining. In part 1 of this study ( 10.1021/acs.jafc.6b00641 ), the reaction of H2S and thiols with Cu(II) was examined; however, the interaction of iron and copper is also known to play an important synergistic role in mediating non-enzymatic wine oxidation. The interaction of these two metals in the oxidation of H2S and thiols (cysteine, 3-sulfanylhexan-1-ol, and 6-sulfanylhexan-1-ol) was therefore examined under wine-like conditions. H2S and thiols (300 μM) were reacted with Fe(III) (100 or 200 μM) alone and in combination with Cu(II) (25 or 50 μM), and concentrations of H2S and thiols, oxygen, and acetaldehyde were monitored over time. H2S and thiols were shown to be slowly oxidized in the presence of Fe(III) alone and were not bound to Fe(III) under model wine conditions. However, Cu(II) added to model wine containing Fe(III) was quickly reduced by H2S and thiols to form Cu(I) complexes, which then rapidly reduced Fe(III) to Fe(II). Oxidation of Fe(II) in the presence of oxygen regenerated Fe(III) and completed the iron redox cycle. In addition, sulfur-derived oxidation products were observed, and the formation of organic polysulfanes was demonstrated.

  9. Iodine transfers in the coastal marine environment: the key role of brown algae and of their vanadium-dependent haloperoxidases. (United States)

    Leblanc, Catherine; Colin, Carole; Cosse, Audrey; Delage, Ludovic; La Barre, Stéphane; Morin, Pascal; Fiévet, Bruno; Voiseux, Claire; Ambroise, Yves; Verhaeghe, Elodie; Amouroux, David; Donard, Olivier; Tessier, Emmanuel; Potin, Philippe


    Brown algal kelp species are the most efficient iodine accumulators among all living systems, with an average content of 1.0% of dry weight in Laminaria digitata, representing a ca. 30,000-fold accumulation of this element from seawater. Like other marine macroalgae, kelps are known to emit volatile short-lived organo-iodines, and molecular iodine which are believed to be a main vector of the iodine biogeochemical cycle as well as having a significant impact on atmospheric chemistry. Therefore, radioactive iodine can potentially accumulate in seaweeds and can participate in the biogeochemical cycling of iodine, thereby impacting human health. From a radioecological viewpoint, iodine-129 (129I, half-life of 1.6 x 10(7) years) is one of the most persistent radionuclide released from nuclear facilities into the environment. In this context, the speciation of iodine by seaweeds is of special importance and there is a need to further understand the mechanisms of iodine uptake and emission by kelps. Recent results on the physiological role and biochemistry of the vanadium haloperoxidases of brown algae emphasize the importance of these enzymes in the control of these processes.

  10. The haloperoxidase of the agaric fungus Agrocybe aegerita hydroxylates toluene and naphthalene. (United States)

    Ullrich, René; Hofrichter, Martin


    The mushroom Agrocybe aegerita secretes a peroxidase (AaP) that catalyzes halogenations and hydroxylations. Phenol was brominated to 2- and 4-bromophenol (ratio 1:4) and chlorinated to a lesser extent to 2-chlorophenol. The purified enzyme was found to oxidize toluene via benzyl alcohol and benzaldehyde into benzoic acid. A second fraction of toluene was hydroxylated to give p-cresol as well as o-cresol and methyl-p-benzoquinone. The UV-Vis absorption spectrum of purified AaP showed high similarity to a resting state cytochrome P450 with the Soret band at 420 nm and additional maxima at 278, 358, 541 and 571 nm; the AaP CO-complex had a distinct absorption maximum at 445 nm that is characteristic for heme-thiolate proteins. AaP regioselectively hydroxylated naphthalene to 1-naphthol and traces of 2-naphthol (ratio 36:1). H2O2 was necessarily required for AaP function and hence the hydroxylations catalyzed by AaP can be designated as peroxygenation and the enzyme as an extracellular peroxygenase.

  11. Iodine-Catalyzed Polysaccharide Esterification (United States)

    A review is provided of the recent reports to use iodine-catalyzed esterification reaction to produce esters from polysaccharides. The process entails reaction of the polysaccharide with an acid anhydride in the presence of a catalytic level of iodine, and in the absence of additional solvents. T...

  12. A lipoxygenase from red alga Pyropia haitanensis, a unique enzyme catalyzing the free radical reactions of polyunsaturated fatty acids with triple ethylenic bonds.

    Directory of Open Access Journals (Sweden)

    Zhujun Zhu

    Full Text Available Lipoxygenases (LOXs are key enzymes to regulate the production of hormones and defensive metabolites in plants, animals and algae. In this research, a full length LOX gene has been cloned and expressed from the red alga Pyropia haitanensis (Bangiales, Rhodophyta gametophyte (PhLOX2. Subsequent phylogenetic analysis showed that such LOX enzymes are separated at the early stage of evolution, establishing an independent branch. The LOX activity was investigated at the optimal pH of 8.0. It appears that PhLOX2 is a multifunctional enzyme featuring both lipoxygenase and hydroperoxidase activities. Additionally, PhLOX2 exhibits remarkable substrate and position flexibility, and it can catalyze an array of chemical reactions involving various polyunsaturated fatty acids, ranging from C18 to C22. As a matter of fact, mono-hydroperoxy, di-hydroperoxy and hydroxyl products have been obtained from such transformations, and eicosapentaenoic acid seem to be the most preferred substrate. It was found that at least triple ethylenic bonds are required for PhLOX2 to function as a LOX, and the resulting hydroxy products should be originated from the PhLOX2 mediated reduction of mono-hydroperoxides, in which the hydrogen abstraction occurs on the carbon atom between the second and third double bond. Most of the di-hydroperoxides observed seem to be missing their mono-position precursors. The substrate and position flexibility, as well as the function versatility of PhLOXs represent the ancient enzymatic pathway for organisms to control intracellular oxylipins.

  13. A lipoxygenase from red alga Pyropia haitanensis, a unique enzyme catalyzing the free radical reactions of polyunsaturated fatty acids with triple ethylenic bonds. (United States)

    Zhu, Zhujun; Qian, Feijian; Yang, Rui; Chen, Juanjuan; Luo, Qijun; Chen, Haimin; Yan, Xiaojun


    Lipoxygenases (LOXs) are key enzymes to regulate the production of hormones and defensive metabolites in plants, animals and algae. In this research, a full length LOX gene has been cloned and expressed from the red alga Pyropia haitanensis (Bangiales, Rhodophyta) gametophyte (PhLOX2). Subsequent phylogenetic analysis showed that such LOX enzymes are separated at the early stage of evolution, establishing an independent branch. The LOX activity was investigated at the optimal pH of 8.0. It appears that PhLOX2 is a multifunctional enzyme featuring both lipoxygenase and hydroperoxidase activities. Additionally, PhLOX2 exhibits remarkable substrate and position flexibility, and it can catalyze an array of chemical reactions involving various polyunsaturated fatty acids, ranging from C18 to C22. As a matter of fact, mono-hydroperoxy, di-hydroperoxy and hydroxyl products have been obtained from such transformations, and eicosapentaenoic acid seem to be the most preferred substrate. It was found that at least triple ethylenic bonds are required for PhLOX2 to function as a LOX, and the resulting hydroxy products should be originated from the PhLOX2 mediated reduction of mono-hydroperoxides, in which the hydrogen abstraction occurs on the carbon atom between the second and third double bond. Most of the di-hydroperoxides observed seem to be missing their mono-position precursors. The substrate and position flexibility, as well as the function versatility of PhLOXs represent the ancient enzymatic pathway for organisms to control intracellular oxylipins.

  14. Iodination of carbohydrate-derived 1,2-oxazines to enantiopure 5-iodo-3,6-dihydro-2H-1,2-oxazines and subsequent palladium-catalyzed cross-coupling reactions

    Directory of Open Access Journals (Sweden)

    Michal Medvecký


    Full Text Available Iodination of carbohydrate-derived 3,6-dihydro-2H-1,2-oxazines of type 3 using iodine and pyridine in DMF furnished 5-iodo-substituted 1,2-oxazine derivatives 4 with high efficacy. The alkenyl iodide moiety of 1,2-oxazine derivatives syn-4 and anti-4 was subsequently exploited for the introduction of new functionalities at the C-5 position by applying palladium-catalyzed carbon–carbon bond-forming reactions such as Sonogashira, Heck, or Suzuki coupling reactions as well as a cyanation reaction. These cross-coupling reactions led to a series of 5-alkynyl-, 5-alkenyl-, 5-aryl- and 5-cyano-substituted 1,2-oxazine derivatives being of considerable interest for further synthetic elaborations. This was exemplarily demonstrated by the hydrogenation of syn-21 and anti-24 and by a click reaction of a 5-alkynyl-substituted precursor.

  15. Haloperoxidase Mediated Quorum Quenching by Nitzschia cf pellucida: Study of the Metabolization of N-Acyl Homoserine Lactones by a Benthic Diatom

    Directory of Open Access Journals (Sweden)

    Michail Syrpas


    Full Text Available Diatoms are known to produce a variety of halogenated compounds, which were recently shown to have a role in allelopathic interactions between competing species. The production of these compounds is linked to haloperoxidase activity. This research, has shown that this system may also be involved in diatom-bacteria interactions via the H2O2 dependent inactivation of a type of quorum sensing (QS molecule, i.e., N-β-ketoacylated homoserine lactones (AHLs, by a natural haloperoxidase system from the benthic diatom Nitzschia cf pellucida. The AHL degradation pathway towards corresponding halogenated derivatives was elucidated via HPLC-MS analysis and the synthesis of a broad series of novel halogenated AHL analogues as reference compounds. Furthermore, their biological activity as quorum sensing modulators was directly compared and evaluated against a series of naturally occurring β-keto-AHLs. It has been demonstrated that the loss of the QS activity results from the final cleavage of the halogenated N-acyl chain of the signal molecules.

  16. The mechanism of an asymmetric ring-opening reaction of epoxide with amine catalyzed by a metal-organic framework: insights from combined quantum mechanics and molecular mechanics calculations. (United States)

    Doitomi, Kazuki; Xu, Kai; Hirao, Hajime


    We applied QM/MM calculations to the asymmetric ring-opening reaction of cyclohexene oxide with aniline catalyzed by a two-dimensional metal-organic framework (MOF) that contains a Cu-paddlewheel (Cu-PDW) unit, aiming to elucidate the reaction mechanism and to identify the factors that determine the enantioselectivity of the reaction. Our QM/MM calculations show that the reaction consists of two major steps. In the first step, ring-opening of the epoxide moiety occurs that leads to an intermediate having an alkoxide ion, and the strong binding of the alkoxide to the Cu(ii) center results in cleavage of one of the four coordination bonds of the copper with carboxylate ligands. In the second step of the reaction, there is a proton transfer from aniline to a distant site-i.e., the alkoxide oxygen atom-to form the β-amino alcohol product, and the carboxylate ligands of the Cu-PDW unit assist this process. The first ring-opening step was calculated as the rate-limiting step, and the enantioselectivity arises from different degrees of CH-π interactions between aniline and a naphthol group in the transition states. The transition state for the ring-opening step in the formation of the (R,R)-isomer is stabilized by CH-π interactions, whereas such interactions are absent in the transition state for the (S,S)-isomer formation. Interestingly, QM/MM calculations also show that the Cu-PDW unit does not maintain a symmetric geometry during the reaction but rather is flexible enough to detach a carboxylate ligand from the copper center, thereby facilitating the reaction. These results illuminate the utility of multiscale QM/MM computations in identifying critical factors determining the reactivity and selectivity of MOF-catalyzed reactions.

  17. Chemoenzymatic halogenation of phenols by using the haloperoxidase from Curvularia inaequalis

    NARCIS (Netherlands)

    Fernández-Fueyo, E.; van Wingerden, M.; Renirie, R.; Wever, R.; Ni, Y.; Holtmann, D.; Hollmann, F.


    The vanadium-​dependent chloroperoxidase from Curvularia inaequalis is an efficient biocatalyst for the in situ generation of hypohalous acids and subsequent electrophilic oxidn.​/halogenation reactions. Esp., its superb activity and stability under operational conditions make it an attractive

  18. Cu(II)-catalyzed acylation by thiol esters under neutral conditions: tandem acylation-wittig reaction leading to a one-pot synthesis of butenolides. (United States)

    Matsuo, Kazumasa; Shindo, Mitsuru


    The first catalytic acylation of alcohols with a thiol ester present in Wittig reagents under neutral conditions catalyzed by the Cu(II) salt through a push-pull mechanism is reported. Furthermore, a new methodology for the one-pot lactonization of acyloins by a copper catalyst is developed. The synthetic utility of this method for the synthesis of natural products is shown.

  19. Three-component reactions of kojic acid: Efficient synthesis of Dihydropyrano[3,2-b]chromenediones and aminopyranopyrans catalyzed with Nano-Bi2O3-ZnO and Nano-ZnO

    Directory of Open Access Journals (Sweden)

    Maryam Zirak


    Full Text Available Synthesis of pyrano-chromenes and pyrano-pyrans was developed by three-component reactions of kojic acid and aromatic aldehydes with dimethone and malononitrile, catalyzed with nano-Bi2O3-ZnO and nano-ZnO, respectively. Reactions proceeded smoothly and the corresponding heterocyclic products were obtained in good to high yields. Nano ZnO and nano Bi2O3-ZnO were prepared by sol-gel method and characterized by X-ray diffraction (XRD, energy-dispersive X-ray analysis (EDX, Fourier transform infrared (FT-IR, scanning electron microscopy (SEM, and transmission electron microscopy (TEM techniques. Supporting Bi3+ on ZnO nanoparticles as Bi2O3, is the main novelty of this work. The simple reaction procedure, easy separation of products, low catalyst loading, reusability of the catalyst are some advantageous of this protocol.

  20. Data on the identification and characterization of by-products from N-Cbz-3-aminopropanal and t-BuOOH/H2O2 chemical reaction in chloroperoxidase-catalyzed oxidations. (United States)

    Masdeu, Gerard; Pérez-Trujillo, Míriam; López-Santín, Josep; Álvaro, Gregorio


    This data article is related to the subject of a publication in Process Biochemistry, entitled "Chloroperoxidase-catalyzed amino alcohol oxidation: Substrate specificity and novel strategy for the synthesis of N-Cbz-3-aminopropanal" (Masdeu et al., 2016) [1]. Here, the products of the chemical reaction involving the amino aldehyde (N-Cbz-3-aminopropanal) and peroxides (tert-butyl hydroperoxide and H2O2) are characterized by NMR. (1)H and (13)C NMR full characterization of the products was obtained based on 2D NMR, 1D selective NOESY and diffusion spectroscopy (DOSY) experiments.

  1. Data on the identification and characterization of by-products from N-Cbz-3-aminopropanal and t-BuOOH/H2O2 chemical reaction in chloroperoxidase-catalyzed oxidations

    Directory of Open Access Journals (Sweden)

    Gerard Masdeu


    Full Text Available This data article is related to the subject of a publication in Process Biochemistry, entitled “Chloroperoxidase-catalyzed amino alcohol oxidation: Substrate specificity and novel strategy for the synthesis of N-Cbz-3-aminopropanal” (Masdeu et al., 2016 [1]. Here, the products of the chemical reaction involving the amino aldehyde (N-Cbz-3-aminopropanal and peroxides (tert-butyl hydroperoxide and H2O2 are characterized by NMR. 1H and 13C NMR full characterization of the products was obtained based on 2D NMR, 1D selective NOESY and diffusion spectroscopy (DOSY experiments.

  2. Gold-catalyzed aerobic epoxidation of trans-stilbene in methylcyclohexane. Part II: Identification and quantification of a key reaction intermediate

    KAUST Repository

    Guillois, Kevin


    The gold-catalyzed aerobic oxidations of alkenes are thought to rely on the in situ synthesis of hydroperoxide species, which have however never been clearly identified. Here, we show direct experimental evidence for the presence of 1-methylcyclohexyl hydroperoxide in the aerobic co-oxidation of stilbene and methylcyclohexane catalyzed by the Au/SiO2-R972 optimized catalyst prepared in Part I. Determination of its response in gas chromatography, by triphenylphosphine titration followed by 31P NMR, allows to easily follow its concentration throughout the co-oxidation process and to clearly highlight the simultaneous existence of the methylcyclohexane autoxidation pathway and the stilbene epoxidation pathway. © 2012 Elsevier B.V. All rights reserved.

  3. Kinetics and mechanism of uncatalyzed and ruthenium(III)-catalyzed ...

    Indian Academy of Sciences (India)

    The effect of ionic strength on both uncatalyzed and catalyzed reactions was studied by varying the. NaClO4 concentration. The rate of uncatalyzed reaction was found to increase with increasing ionic strength, whereas the rate of catalyzed reaction decreases with the increase of ionic strength. Thus, the plot of ln kU.

  4. Can laccases catalyze bond cleavage in lignin?

    DEFF Research Database (Denmark)

    Munk, Line; Sitarz, Anna Katarzyna; Kalyani, Dayanand


    these enzymes may help degrading lignin, using oxygen as the oxidant. Laccases can catalyze polymerization of lignin, but the question is whether and how laccases can directly catalyze modification of lignin via catalytic bond cleavage. Via a thorough review of the available literature and detailed...... illustrations of the putative laccase catalyzed reactions, including the possible reactions of the reactive radical intermediates taking place after the initial oxidation of the phenol-hydroxyl groups, we show that i) Laccase activity is able to catalyze bond cleavage in low molecular weight phenolic lignin...... model compounds; ii) For laccases to catalyze inter-unit bond cleavage in lignin substrates, the presence of a mediator system is required. Clearly, the higher the redox potential of the laccase enzyme, the broader the range of substrates, including o- and p-diphenols, aminophenols, methoxy...

  5. Production of L-malic acid with fixation of HCO3(-) by malic enzyme-catalyzed reaction based on regeneration of coenzyme on electrode modified by layer-by-layer self-assembly method. (United States)

    Zheng, Haitao; Ohno, Yoko; Nakamori, Toshihiko; Suye, Shin-Ichiro


    Malic enzyme prepared and purified from Brevundimonas diminuta IFO13182 catalyzed the decarboxylation reaction of malate to pyruvate and CO2 using NAD+ as the coenzyme, and the reverse reaction was used in the present study for L-malic acid production with fixation of HCO3(-) as a model compound for carbon source. The L-malic acid production was based on electrochemical regeneration of NADH on a carbon plate electrode modified by layer-by-layer adsorption of polymer-bound mediator (Alginic acid bound viologen derivative, Alg-V), polymer-bound coenzyme (Alginic acid bound NAD+, Alg-NAD+), and lipoamide dehydrogenase (LipDH). Electrochemical reduction of immobilized NAD+ catalyzed by LipDH in a multilayer film was achieved, and the L-malic acid production with HCO3(-) fixation system with layer-by-layer immobilization of Alg-V/LipDH/Alg-NAD+/malic enzyme multilayer film on the electrode gave an L-malic acid production of nearly 11.9 mmol and an HCO3(-) fixation rate of nearly 47.4% in a buffer containing only KHCO3 and pyruvic acid potassium salt, using a cation exchange membrane. The total turnover number of NADH within 48 h was about 19,000, which suggests that efficient NADH regeneration and fast electron transfer were achieved within the multilayer film, and that the modified electrode is a potential method for the fixation of HCO3(-) without addition of free coenzyme.

  6. Lipase-catalyzed asymmetric synthesis of naphtho[2,3-c]furan-1(3H)-one derivatives by a one-pot dynamic kinetic resolution/intramolecular Diels-Alder reaction: Total synthesis of (-)-himbacine. (United States)

    Sugiyama, Koji; Kawanishi, Shinji; Oki, Yasuhiro; Kamiya, Marin; Hanada, Ryosuke; Egi, Masahiro; Akai, Shuji


    One-pot sequential reactions using the acyl moieties installed by enzymatic dynamic kinetic resolution of alcohols have been little investigated. In this work, the acryloyl moiety installed via the lipase/oxovanadium combo-catalyzed dynamic kinetic resolution of a racemic dienol [4-(cyclohex-1-en-1-yl)but-3-en-2-ol or 1-(cyclohex-1-en-1-yl)but-2-en-1-ol] with a (Z)-3-(phenylsulfonyl)acrylate underwent an intramolecular Diels-Alder reaction in a one-pot procedure to produce an optically active naphtho[2,3-c]furan-1(3H)-one derivative (98% ee). This method was successfully applied to the asymmetric total synthesis of (-)-himbacine. Copyright © 2017 Elsevier Ltd. All rights reserved.

  7. SnCl(4)- and TiCl(4)-catalyzed anomerization of acylated O- and S-glycosides: analysis of factors that lead to higher α:β anomer ratios and reaction rates. (United States)

    Pilgrim, Wayne; Murphy, Paul V


    The quantification of factors that influence both rates and stereoselectivity of anomerization reactions catalyzed by SnCl(4) and TiCl(4) and how this has informed the synthesis of α-O- and α-S-glycolipids is discussed. The SnCl(4)-catalyzed anomerization reactions of β-S- and β-O-glycosides of 18 substrates followed first order equilibrium kinetics and k(f) + k(r) values were obtained, where k(f) is the rate constant for the forward reaction (β → α) and k(r) is the rate constant for the reverse reaction (α → β). Comparison of the k(f) + k(r) values showed that reactions of glucuronic acid or galacturonic acid derivatives were ∼10 to 3000 times faster than those of related glucoside and galactopyranoside counterparts and α:β ratios were generally also higher. Stereoelectronic effects contributed from galacto-configured compounds were up to 2-fold faster than those of corresponding glucosides. The introduction of groups, including protecting groups, which are increasingly electron releasing generally led to rate enhancements. The anomerization of S-glycosides was consistently faster than that of corresponding O-glycosides. Reactions were generally faster for reactions with TiCl(4) than those with SnCl(4). Anomeric ratios depended on the Lewis acid, the number equivalents of the Lewis acid, temperature, and substrate. Very high ratios of α-products for both O- and S-glucuronides were observed for reactions promoted by TiCl(4); for these substrates TiCl(4) was superior to SnCl(4). Anomeric ratios from anomerization of S-glucosides were higher with SnCl(4) than with TiCl(4). The dependence of equilibrium ratio on Lewis acid and the number of equivalents of Lewis acid indicated that the equilibrium ratio is determined by a complex of the saccharide residue bound to the Lewis acid and not the free glycoside. The high α:β ratios observed for anomerization of both O- and S-glycuronic acids can be explained by coordination of the C-1 heteroatom and C-6

  8. Iodine(III)-Catalyzed Cascade Reactions Enabling a Direct Access to β-Lactams and α-Hydroxy-β-amino Acids. (United States)

    Patzelt, Christoph; Pöthig, Alexander; Gulder, Tanja


    In the presented method, a one-pot metal-free access to β-lactams is provided. The developed strategy employs a hypervalent iodine(III)-triggered bromination/rearrangement/cyclization cascade reaction that allows the straightforward synthesis of a broad range of structurally different lactams from cheap and easily available imides. This triple cascade reaction is furthermore extendable by an in situ ring-opening reaction, giving direct access to isoserine derivatives from simple imines in a four-step, one-pot reaction.

  9. Lipase-catalyzed domino kinetic resolution/intramolecular Diels-Alder reaction: one-pot synthesis of optically active 7-oxabicyclo[2.2.1]heptenes from furfuryl alcohols and beta-substituted acrylic acids. (United States)

    Akai, Shuji; Naka, Tadaatsu; Omura, Sohei; Tanimoto, Kouichi; Imanishi, Masashi; Takebe, Yasushi; Matsugi, Masato; Kita, Yasuyuki


    The first lipase-catalyzed domino reaction is described in which the acyl moiety formed during the enzymatic kinetic resolution of furfuryl alcohols (+/-)-3 with a 1-ethoxyvinyl ester 2 was utilized as a part of the constituent structure for the subsequent Diels-Alder reaction. The preparation of ester 2 from carboxylic acid 1 and the subsequent domino reaction were carried out in a one-pot reaction. Therefore, this procedure provides a convenient preparation of the optically active 7-oxabicyclo[2.2.1]heptene derivatives 5, which has five chiral, non-racemic carbon centers, from achiral 1 and racemic 3. The overall efficiency of this process was dependent on the substituent at the C-3 position of 3, and the use of the 3-methylfurfuryl derivatives, (+/-)-3 b and (+/-)-3 f, exclusively produced diastereoselectivity with excellent enantioselectivity to give (2R)-syn-5 (91->/=99 % ee) and (S)-3 (96->/=99 % ee). Similar procedures starting from the 3-bromofurfuryl alcohols (+/-)-3 h-j provided the cycloadducts (2R)-syn-5 j-q (93->/=99 % ee), in which the bromo group was utilized for the installation of bulky substituents to the 7-oxabicycloheptene core.

  10. Catalysis of Photochemical Reactions. (United States)

    Albini, A.


    Offers a classification system of catalytic effects in photochemical reactions, contrasting characteristic properties of photochemical and thermal reactions. Discusses catalysis and sensitization, examples of catalyzed reactions of excepted states, complexing ground state substrates, and catalysis of primary photoproducts. (JM)

  11. Enantioselective Cu-II-Catalyzed Diels-Alder and Michael Addition Reactions in Water Using Bio-Inspired Triazacyclophane-Based Ligands

    NARCIS (Netherlands)

    Albada, H. Bauke; Rosati, Fiora; Coquiere, David; Roelfes, Gerard; Liskamp, Rob M. J.

    A triazacyclophane (TAC) scaffold decorated with three histidine amino acid residues was used as a tridentate ligand in asymmetric copper(II)-catalysed Diels-Alder and Michael addition reactions in water. Enantiomeric excesses up to 55% were obtained in Diels-Alder reactions using ligands in which

  12. Alpha,beta-unsaturated delta-lactones from copper-catalyzed asymmetric vinylogous Mukaiyama reactions of aldehydes: scope and mechanistic insights. (United States)

    Bazán-Tejeda, Belén; Bluet, Guillaume; Broustal, Garance; Campagne, Jean-Marc


    A direct regio-, diastereo-, and enantiocontrolled access to alpha,beta-unsaturated delta-lactones is described, based on the reaction of a silyl dienolate and an aldehyde in the presence of 10 % of Carreira's catalyst. The scope and limitations of this reaction, as well as mechanistic insights concerning the reactivity of an allyl copper species, are discussed.

  13. Cu(I)/Rh(II)-Catalyzed Tandem Convergent Multicomponent Reaction for the Regio- and Stereocontrolled Synthesis of γ-Oxo-β-amino Esters. (United States)

    Jung, Da Jung; Jeon, Hyun Ji; Lee, Joo Hyun; Lee, Sang-gi


    The first example of a highly regio- and stereoselective catalytic method for the three-component one-pot synthesis of highly functionalized α-vinylated γ-oxo-β-amino esters is disclosed. In this catalytic triad, the Cu(I)-catalyst selectively catalyzes the cycloaddition of the 1-alkyne and sulfonyl azide first resulting in the corresponding 1-sulfonyl-1,2,3-triazole. An α-imino Rh(II)-carbene is generated from an open-chain α-imino diazo of the triazole, and this species reacts with γ-hydroxy α,β-unsaturated esters to form allylic (Z)-amino vinyl ethers. Rapid deconjugative [3,3]-sigmatropic rearrangement affords the α-vinyl γ-oxo-β-amino esters in high yields with high levels of diastereoselectivity.

  14. (Trans)esterification of mannose catalyzed by lipase B from Candida antarctica in an improved reaction medium using co-solvents and molecular sieve. (United States)

    Nott, Katherine; Brognaux, Alison; Richard, Gaëtan; Laurent, Pascal; Favrelle, Audrey; Jérôme, Christine; Blecker, Christophe; Wathelet, Jean-Paul; Paquot, Michel; Deleu, Magali


    Four co-solvents (dimethylformamide [DMF], formamide, dimethyl sulfoxide [DMSO], and pyridine) were tested with tert-butanol (tBut) to optimize the initial rate (v₀) and yield of mannosyl myristate synthesis by esterification catalyzed by immobilized lipase B from Candida antarctica. Ten percent by volume of DMSO resulted in the best improvement of v₀ and 48-hr yield (respectively 115% and 13% relative gain compared to pure tBut). Use of molecular sieve (5% w/v) enhances the 48-hr yield (55% in tBut/DMSO [9:1, v/v]). Transesterification in tBut/DMSO (9:1, v/v) with vinyl myristate leads to further improvement of v₀ and 48-hr yield: a relative gain of 85% and 65%, respectively, without sieve and 25% and 10%, respectively, with sieve, compared to esterification. No difference in v₀ and 48-hr yield is observed when transesterification is carried out with or without sieve.

  15. Studies on Pd/NiFe2O4 catalyzed ligand-free Suzuki reaction in aqueous phase: synthesis of biaryls, terphenyls and polyaryls

    Directory of Open Access Journals (Sweden)

    Suresh B. Waghmode


    Full Text Available Palladium supported on nickel ferrite (Pd/NiF2O4 was found to be a highly active catalyst for the Suzuki coupling reaction between various aryl halides and arylboronic acids. The reaction gave excellent yields (70–98% under ligand free conditions in a 1:1 DMF/H2O solvent mixture, in short reaction times (10–60 min. The catalyst could be recovered easily by applying an external magnetic field. The polyaryls were similarly synthesized.

  16. Production of edible carbohydrates from formaldehyde in a spacecraft. pH variations in the calcium hydroxide catalyzed formose reaction. Final Report, 1 Jul. 1973 - 30 Jun. 1974. M.S. Thesis (United States)

    Weiss, A. H.; Kohler, J. T.; John, T.


    The study of the calcium hydroxide catalyzed condensation of formaldehyde was extended to a batch reactor system. Decreases in pH were observed, often in the acid regime, when using this basic catalyst. This observation was shown to be similar to results obtained by others using less basic catalysts in the batch mode. The relative rates of these reactions are different in a batch reactor than in a continuous stirred tank reactor. This difference in relative rates is due to the fact that at any degree of advancement in the batch system, the products have a history of previous products, pH, and dissolved catalyst. The relative rate differences can be expected to yield a different nature of product sugars for the two types of reactors.

  17. Highly Enantioselective Construction of Tertiary Thioethers and Alcohols via Phosphine-Catalyzed Asymmetric γ-Addition reactions of 5H-Thiazol-4-ones and 5H-Oxazol-4-ones: Scope and Mechanistic Understandings

    KAUST Repository

    Wang, Tianli


    Phosphine-catalyzed highly enantioselective γ-additions of 5H-thiazol-4-ones and 5H-oxazol-4-ones to allenoates have been developed for the first time. With the employment of amino-acid derived bifunctional phosphines, a wide range of substituted 5H-thiazol-4-one and 5H-oxazol-4-one derivatives bearing heteroarom (S or O)-containing tertiary chiral centers were constructed in high yields and excellent enantioselectivities. The reported method provides a facile access to enantioenriched tertiary thioether/alcohols. The mechanism of γ-addition reaction was investigated by performing DFT calculations, and the hydrogen bonding interactions between the Brønsted acid moiety of the phosphine catalysts and the “C=O” unit of donor molecules were shown to be crucial in asymmetric induction.

  18. Another Role of Copper in the Simmons–Smith Reaction: Copper-catalyzed Nucleophilic Michael-type Cyclopropanation of α,β-Unsaturated Ketones

    National Research Council Canada - National Science Library

    Fujii, Kanami; Misaki, Tomonori; Sugimura, Takashi


    .... The reaction was performed in the presence of a copper salt. The reactivity was highly dependent on the substrate structure, and cyclopropanated products were obtained in better yields than those achieved using the original Simmons...

  19. A theoretical investigation on the Strecker reaction catalyzed by a Ti(IV)-complex catalyst generated from a cinchona alkaloid, achiral substituted 2,2'-biphenol, and tetraisopropyl titanate. (United States)

    Su, Zhishan; Li, Weiyi; Wang, Jun; Hu, Changwei; Feng, Xiaoming


    The mechanism and the origin of selectivity of the asymmetric Strecker reaction catalyzed by a Ti(IV)-complex catalyst generated from a cinchona alkaloid, achiral substituted 2,2'-biphenol, and tetraisopropyl titanate have been investigated by DFT and ONIOM methods. The calculations indicate that the reaction proceeds through a dual activation mechanism, in which Ti(IV) acts as Lewis acid to activate the electrophile aldimine substrate, whereas the tertiary amine in cinchona alkaloid works as Lewis base to promote the activation and isomerization of HCN. The C-C bond formation step is predicted to be the selectivity-controlling step in the reaction with an energy barrier of 9.3 kcal mol(-1). The "asymmetric activation" is achieved by the transfer of asymmetry from the chiral cinchonine ligand to the axially flexible achiral biphenol ligand through coordination interaction with the central metal Ti(IV) . The large steric hindrance from the 3,3'-position substitute of biphenol, combined with the quinoline fragment of cinchona alkaloid and the orientation of hydrogen bonding of iPrOH, play a key role in controlling the stereoselectivity, which is in good agreement with the experimental observations. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Effect of halo-substituted aromatic salts on counterion binding constants obtained from cationic nanoparticle catalyzed reactions of piperidine and phenyl salicylate (United States)

    Fagge, Ibrahim I.; Yusof, Nor Saadah M.; Zain, Sharifuddin Md; Khan, M. Niyaz


    Halo-substitutions at 3-position of benzene ring of the salts of aromatic carboxylate, MX, revealed the effect of two different halide ions (Br- and Cl-) on the counterion binding constants obtained from cationic nanoparticle catalyzed piperidinolysis of ionized phenyl salicylate (PhS-). The values of observed rate constant, kobs, determined at a constant total concentration of cetyltrimethylammonium bromide, [CTABr]T, piperidine, ([P]T), [PhS-]T, NaOH, and various concentration of MX (MX = 3-BrC6H4CO2Na and 3-ClC6H4CO2Na), were determined using UV-visible X spectrophotometric technique at 35 °C and 370 nm. The average value of nanoparticle binding constant, KXBr, for X- = 3-BrC6H4CO2- (RXBr = 57) was found to be about 2-fold larger than that for X- = 3-ClC6H4CO2- (RXBr = 30). These XX values were dependent of substituents 3-Br and 3-Cl, and independent of [CTABr]T. Both are related to the presence of different extent of viscoelastic worm-like nanoparticles formation in the [CTABr]T of 6 and 10 mM.

  1. One-Pot Multicomponent Synthesis of Glycopolymers through a Combination of Host-Guest Interaction, Thiol-ene, and Copper-Catalyzed Click Reaction in Water. (United States)

    Hu, Xiang; Gao, Jinbo; Luo, Yan; Wei, Ting; Dong, Yishi; Chen, Gaojian; Chen, Hong


    There is a common phenomenon that the heterogeneity of natural oligosaccharides contains various sugar units, which can be used to enhance affinity and selectivity toward a specific receptor, so the synthesis of heterogeneous glycopolymers is always an important issue in the glycopolymer field. Herein, this study conducts a one-pot method to prepare polyrotaxane-based heteroglycopolymers anchored with different sugar units and fluorescent moieties via the combination of host-guest interaction, thiol-ene, and copper-catalyzed click chemistry in water. Fourier transform infrared spectroscopy, nuclear magnetic resonance spectroscopy, gel permeation chromatography, X-ray diffraction, and Ellman's assay test are used in the paper to characterize the compounds. Quartz crystal microbalance-dissipation (QCD-D) experiments and bacterial adhesion assay are utilized to study the interactions of polyrotaxane-based heteroglycopolymers with Con A and Escherichia coli. The results reveal that polyrotaxanes (PRs) with mannose and glucose present better specificity toward Con A and E. coli than PRs with glucose due to synergistic effects. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Petasis Borono-Mannich reaction and allylation of carbonyl compounds via transient allyl boronates generated by palladium-catalyzed substitution of allyl alcohols. an efficient one-pot route to stereodefined alpha-amino acids and homoallyl alcohols. (United States)

    Selander, Nicklas; Kipke, Andreas; Sebelius, Sara; Szabó, Kalman J


    An efficient one-pot procedure was designed by integration of the pincer-complex-catalyzed borylation of allyl alcohols in the Petasis borono-Mannich reaction and in allylation of aldehydes and ketones. These procedures are suitable for one-pot synthesis of alpha-amino acids and homoallyl alcohols from easily available allyl alcohol, amine, aldehyde, or ketone substrates. In the presented transformations, the active allylating agents are in situ generated allyl boronic acid derivatives. These transient intermediates are proved to be reasonably acid-, base-, alcohol-, water-, and air-stable species, which allows a high level of compatibility with the reaction conditions of the allylation of various aldehyde/ketone and imine electrophiles. The boronate source of the reaction is diboronic acid or in situ hydrolyzed diboronate ester ensuring that the waste product of the reaction is nontoxic boric acid. The regio- and stereoselectivity of the reaction is excellent, as almost all products form as single regio- and stereoisomers. The described procedure is suitable to create quaternary carbon centers in branched allylic products without formation of the corresponding linear allylic isomers. Furthermore, products comprising three stereocenters were formed as single products without formation of other diastereomers. Because of the highly disciplined consecutive processes, up to four-step, four-component transformations could be performed selectively as a one-pot sequence. For example, stereodefined pyroglutamic acid could be prepared from a simple allyl alcohol, a commercially available amine, and glyoxylic acid in a one-step procedure. The presented method also grants an easy access to stereodefined 1,7-dienes that are useful substrates for Grubbs ring-closing metathesis.

  3. Biodiesel production by enzyme-catalyzed transesterification


    Stamenković Olivera S.; Lazić Miodrag L.; Veljković Vlada B.; Skala Dejan U.


    The principles and kinetics of biodiesel production from vegetable oils using lipase-catalyzed transesterification are reviewed. The most important operating factors affecting the reaction and the yield of alkyl esters, such as: the type and form of lipase, the type of alcohol, the presence of organic solvents, the content of water in the oil, temperature and the presence of glycerol are discussed. In order to estimate the prospects of lipase-catalyzed transesterification for industrial appli...

  4. Build/Couple/Pair Strategy Combining the Petasis 3-Component Reaction with Ru-Catalyzed Ring-Closing Metathesis and Isomerization

    DEFF Research Database (Denmark)

    Ascic, Erhad; Le Quement, Sebastian Thordal; Ishøy, Mette


    A “build/couple/pair” pathway for the systematic synthesis of structurally diverse small molecules is presented. The Petasis 3-component reaction was used to synthesize anti-amino alcohols displaying pairwise reactive combinations of alkene moieties. Upon treatment with a ruthenium alkylidene-cat......-catalyst, these dienes selectively underwent ring-closing metathesis reactions to form 5- and 7-membered heterocycles and cyclic aminals via a tandem isomerization/N-alkyliminium cyclization sequence.......A “build/couple/pair” pathway for the systematic synthesis of structurally diverse small molecules is presented. The Petasis 3-component reaction was used to synthesize anti-amino alcohols displaying pairwise reactive combinations of alkene moieties. Upon treatment with a ruthenium alkylidene...

  5. Asymmetric Michael addition reactions of 3-substituted benzofuran-2(3H)-ones to nitroolefins catalyzed by a bifunctional tertiary-amine thiourea. (United States)

    Li, Xin; Xue, Xiao-Song; Liu, Cong; Wang, Bin; Tan, Bo-Xuan; Jin, Jia-Lu; Zhang, Yue-Yan; Dong, Nan; Cheng, Jin-Pei


    The current work reports an organocatalytic strategy for the asymmetric catalysis of chiral benzofuran-2(3H)-ones bearing 3-position all-carbon quaternary stereocenters. Accordingly, highly enantioselective Michael addition reactions of 3-substituted benzofuran-2(3H)-ones to nitroolefins have been developed by utilizing a bifunctional tertiary-amine thiourea catalyst. The reactions accommodate a number of nitroolefins and 3-substituted benzofuran-2(3H)-ones to give the desired chiral benzofuran-2(3H)-one products with moderate to excellent yields (up to 98%) and moderate to very good selectivities (up to 19 : 1 dr and up to 91% ee). Theoretical calculations using the DFT method on the origin of the stereoselectivity were conducted. The effect of the nitroolefin substituent position on the stereoselectivity of the Michael addition reaction was also theoretically rationalized.

  6. The origin of enantioselectivity in the l-threonine-derived phosphine-sulfonamide catalyzed aza-Morita-Baylis-Hillman reaction: Effects of the intramolecular hydrogen bonding

    KAUST Repository

    Lee, Richmond


    l-Threonine-derived phosphine-sulfonamide 4 was identified as the most efficient catalyst to promote enantioselective aza-Morita-Baylis-Hillman (MBH) reactions, affording the desired aza-MBH adducts with excellent enantioselectivities. Density functional theory (DFT) studies were carried out to elucidate the origin of the observed enantioselectivity. The importance of the intramolecular N-H⋯O hydrogen-bonding interaction between the sulfonamide and enolate groups was identified to be crucial in inducing a high degree of stereochemical control in both the enolate addition to imine and the subsequent proton transfer step, affording aza-MBH reactions with excellent enantioselectivity. © 2013 The Royal Society of Chemistry.

  7. Transition-metal catalyzed synthesis of Ketoprofen

    Directory of Open Access Journals (Sweden)

    Ramminger Carolina


    Full Text Available Transition metal-catalyzed reactions including carbonylations, hydrovinylations and hydrogenations have been applied in the synthesis of alpha-(3-benzoylphenylpropanoic acid (Ketoprofen. 3-Vinylbenzophenone was obtained from 3-bromobenzophenone by a Pd-catalyzed Heck coupling reaction. Pd-catalyzed carbonylation of this olefin gave the isopropyl alpha-(3-benzoylphenyl propionate in high yield (95% and with high regioselectivity (>99.5%. Ketoprofen was obtained in 90% yield by hydrolysis of the isopropyl ester. It was also obtained in two steps from 3-vinylbenzophenone by a Ni-catalyzed hydrovinylation selectively affording 3-(3'-benzoylphenyl-1-butene, followed by an oxidation. 3-Ethynylbenzophenone was obtained from 3-bromobenzophenone by Pd-catalyzed coupling reaction. By means of a Pd-catalyzed carbonylation, this alkyne was converted regioselectively (97% into methyl alpha-(3-benzoylphenyl acrylate (93% yield. Hydrolysis of the ester afforded the alpha-(3-benzoylphenylacrylic acid. Asymmetric hydrogenation of this acid to give (S-ketoprofen in 95% optical yield was achieved using a chiral Ru-(S-BINAP catalyst.

  8. Cu catalyzed oxidation of 5-hydroxymethylfurfural to 2,5-diformylfuran and 2,5-furandicarboxylic acid under benign reaction conditions

    DEFF Research Database (Denmark)

    Hansen, Thomas S.; Sádaba, Irantzu; Garcia, Eduardo


    containing promoters (NCPs) to obtain excellent yields. In acetonitrile a 95% DFF yield was obtained after 24h with ambient pressure of dioxygen at room temperature in the presence of different NCPs, which – to our knowledge – is the best result reported thus far for this reaction. The use of NCPs made...


    The use of solid-liquid phase transfer catalysis has an advantage of carrying out reaction between two immiscible substrates, one in solid phase and the other in liquid phase, with high selectivity and at relatively low temperatures. In this study we investigated the synthesis ci...

  10. Synthesis of 1-amidoalkyl-2-naphthols based on a three-component reaction catalyzed by boric acid as a solid heterogeneous catalyst under solvent-free conditions

    Directory of Open Access Journals (Sweden)

    Zahed Karimi-Jaberi


    Full Text Available An efficient method for the preparation of 1-amidoalkyl-2-naphthols has been described using a multi-component, one-pot condensation reaction of 2-naphthol, aldehydes and amides in the presence of boric acid under solvent-free conditions.DOI:

  11. Quantum tunneling during interstellar surface-catalyzed formation of water: the reaction H + H2O2 → H2O + OH. (United States)

    Lamberts, Thanja; Samanta, Pradipta Kumar; Köhn, Andreas; Kästner, Johannes


    The final step of the water formation network on interstellar grain surfaces starting from the H + O2 route is the reaction between H and H2O2. This reaction is known to have a high activation energy and therefore at low temperatures it can only proceed via tunneling. To date, however, no rate constants are available at temperatures below 200 K. In this work, we use instanton theory to compute rate constants for the title reaction with and without isotopic substitutions down to temperatures of 50 K. The calculations are based on density functional theory, with additional benchmarks for the activation energy using unrestricted single-reference and multireference coupled-cluster single-point energies. Gas-phase bimolecular rate constants are calculated and compared with available experimental data not only for H + H2O2 → H2O + OH, but also for H + H2O2 → H2 + HO2. We find a branching ratio where the title reaction is favored by at least two orders of magnitude at 114 K. In the interstellar medium this reaction predominantly occurs on water surfaces, which increases the probability that the two reactants meet. To mimic this, one, two, or three spectator H2O molecules are added to the system. Eley-Rideal bimolecular and Langmuir-Hinshelwood unimolecular rate constants are presented here. The kinetic isotope effects for the various cases are compared to experimental data as well as to expressions commonly used in astrochemical models. Both the rectangular barrier and the Eckart approximations lead to errors of about an order of magnitude. Finally, fits of the rate constants are provided as input for astrochemical models.

  12. Efficient C-O and C-N bond forming cross-coupling reactions catalyzed by core-shell structured Cu/Cu2O nanowires

    KAUST Repository

    Elshewy, Ahmed M.


    Oxygen and Nitrogen containing compounds are of utmost importance due to their interesting and diverse biological activities. The construction of the C-O and C–N bonds is of significance as it opens avenues for the introduction of ether and amine linkages in organic molecules. Despite significant advancements in this field, the construction of C-O and C–N bonds is still a major challenge for organic chemists, due to the involvement of harsh reaction conditions or the use of expensive catalysts or ligands in many cases. Thus, it is a challenge to develop alternative, milder, cheaper and more reproducible methodologies for the construction of these types of bonds. Herein, we introduce a new efficient ligand free catalytic system for C-O and C-N bond formation reactions.

  13. Cinchona Alkaloid Derivative-Catalyzed Enantioselective Synthesis via a Mannich-Type Reaction and Antifungal Activity of β-Amino Esters Bearing Benzoheterocycle Moieties

    Directory of Open Access Journals (Sweden)

    Han Xiao


    Full Text Available An efficient synthesis of highly functionalized chiral β-amino ester derivatives containing benzothiophene and benzothiazole moieties is developed by a Mannich-type reaction using a cinchona alkaloid-derived thiourea catalyst. The desired products were obtained in good yields and high enantioselectivities (~86% yield, >99% ee using to the optimized reaction conditions. The synthesized compounds were characterized by 1H-NMR, 13C-NMR, IR, and HREI-MS analyses. The bioassays identified that compound 5dr has excellent antifungal activity, with a 60.53% inhibition rate against F. oxysporum, higher than that of the commercial agricultural fungicide hymexazol, whose inhibition rate was 56.12%.

  14. Novel tridentate diamino organomanganese(II) complexes as homogeneous catalysts in manganese(II)/copper(I) catalyzed carbon-carbon bond forming reactions

    NARCIS (Netherlands)

    Koten, G. van; Donkervoort, J.G.; Vicario, J.L.; Jastrzebski, J.T.B.H.; Gossage, R.A.; Cahiez, G.


    The new, paramagnetic arylmanganese(II) complex Li[MnCl2(NCN)] (2, NCN [C6H3(CH2NMe2)2-2,6]−) has been obtained in high yield from the reaction of MnCl2 and [Li(NCN)]2 in a 2:1 molar ratio. In THF solution, 2 is likely an ionic species [Li(THF)n] [MnCl2(NCN)] (molecular weight determination and

  15. Asymmetric NHC-catalyzed aza-Diels-Alder reactions: Highly enantioselective route to α-amino acid derivatives and DFT calculations

    KAUST Repository

    Yang, Limin


    A facile N-heterocyclic carbene catalytic enantioselective aza-Diels-Alder reaction of oxodiazenes with α-chloroaldehydes as dienophile precursors is reported, with excellent enantioselectivity (ee > 99%) and excellent yield (up to 93%). DFT study showed that cis-TSa, formed from a top face approach of oxodiazene to cis-IIa, is the most favorable transition state and is consistent with the experimental observations. © 2014 American Chemical Society.

  16. Microwave-Assisted Condensation Reactions of Acetophenone Derivatives and Activated Methylene Compounds with Aldehydes Catalyzed by Boric Acid under Solvent-Free Conditions. (United States)

    Brun, Elodie; Safer, Abdelmounaim; Carreaux, François; Bourahla, Khadidja; L'helgoua'ch, Jean-Martial; Bazureau, Jean-Pierre; Villalgordo, Jose Manuel


    We here disclosed a new protocol for the condensation of acetophenone derivatives and active methylene compounds with aldehydes in the presence of boric acid under microwave conditions. Implementation of the reaction is simple, healthy and environmentally friendly owing to the use of a non-toxic catalyst coupled to a solvent-free procedure. A large variety of known or novel compounds have thus been prepared, including with substrates bearing acid or base-sensitive functional groups.

  17. Microwave-Assisted Condensation Reactions of Acetophenone Derivatives and Activated Methylene Compounds with Aldehydes Catalyzed by Boric Acid under Solvent-Free Conditions

    Directory of Open Access Journals (Sweden)

    Elodie Brun


    Full Text Available We here disclosed a new protocol for the condensation of acetophenone derivatives and active methylene compounds with aldehydes in the presence of boric acid under microwave conditions. Implementation of the reaction is simple, healthy and environmentally friendly owing to the use of a non-toxic catalyst coupled to a solvent-free procedure. A large variety of known or novel compounds have thus been prepared, including with substrates bearing acid or base-sensitive functional groups.

  18. Kinetic studies on the activation of human factor X. The role of metal ions on the reaction catalyzed by the venom coagulant protein of Viper russelli. (United States)

    Morris, S; Robey, F A; Kosow, D P


    The effect of Ca2+, Mg2+, and Mn2+ on the initial rate of activation of human Factor X by the venom coagulant protein of Vipera russelli has been investigated. Neither Mg2+ nor Mn2+ alone support the reaction. Ca2+ is an essential activator and exhibits cooperative kinetics. Both Mg2+ and Mn2+ enhance the reaction cooperatively when Ca2+ is present at suboptimal concentrations. Similarly, Ca2+ quenches the intrinsic fluorescence of human Factor X in a cooperative manner. While neither Mg2+ nor Mn2+ by themselves affect the fluorescence of human Factor X, they decrease the cooperativity of the Ca2+ binding to the protein as judged by Hill plots of the Ca2+ -induced fluoresence quenching. EPR measurements indicate that there are three high affinity Mn2+ binding sites on human Factor X which can also bind Ca2+. Positive cooperativity was not observed for Mn2+ binding. These data indicate that Ca2+ can cause a conformational change of the Factor X molecule which allows the activation reaction to proceed. We propose that Mn2+ does not support the activation of human Factor X because it cannot induce a necessary conformational change in the absence of Ca2+.

  19. Mechanistic Study of Ni/CeO{sub 2}-catalyzed CO{sub 2}/CH{sub 4} Reaction Using Flow and Static Methods

    Energy Technology Data Exchange (ETDEWEB)

    Kang, Jin-Gyu; Roh, Joong-Seok; Kim, Ji-Yeong; Lee, Sung-Han; Choi, Jonng-Gill [Yonsei University, Seoul (Korea, Republic of)


    Ni/CeO{sub 2} catalysts with different Ni loadings (5, 7, 10, 12, and 14 wt% Ni) were prepared by an impregnation method and examined for the CO{sub 2} reforming of methane using flow and static reactors. Their catalytic activities and selectivities were measured under CO{sub 2}/CH{sub 4}/Ar (=5/5/40 cm{sup 3}/min) flow at 450-800 .deg. C using a flow reactor system with an on-line gas chromatography. At flexed temperature, the CO{sub 2} and CH{sub 4} conversions varied only slightly with the Ni wt%, whereas the H{sub 2}/CO ratio increased with increasing Ni wt%. The conversions increased with temperature, reaching 98% at 800 .deg. C. The H{sub 2}/CO ratio varied with temperature in the range of 450-800 .deg. C, from less than 1 below 550 .deg. C to close to 1 at 550-600 .deg. C and then back to less than 1 above 600 .deg. C. The apparent activation energies were determined to be 43.1 kJ/mol for the CO{sub 2} consumption and 50.2 kJ/mol for the CH{sub 4} consumption based on the rates measured for the reforming reaction over 5 wt% Ni/CeO{sub 2} catalyst at 550-750 .deg. C. Additionally, the catalytic reforming reaction at low pressure (40 Torr) was investigated by a static reactor system by using a differential photoacoustic cell, in which the rates were measured from the CO{sub 2} photoacoustic signal data at early reaction times over the temperature range of 460-610 .deg. C. Apparent activation energies of 25.5-30.1 kJ/mol were calculated from the CO{sub 2} disappearance rates. The CO{sub 2} adsorption on the Ni/CeO{sub 2} catalyst was investigated by the CO{sub 2} photoacoustic spectroscopy and Fourier transform infrared spectroscopy. Feasible side reactions during the catalytic CO{sub 2}/CH{sub 4} reaction were suggested on the basis of the kinetic and spectroscopic results.

  20. Nickel-catalyzed carbocyanation of alkynes


    Nakao, Yoshiaki; Hiyama, Tamejiro


    Nickel-catalyzed carbocyanation reaction of alkynes is described. Alkynes undergo aryl- and allylcyanation reaction in the presence of nickel-phosphine catalysts to give a wide range of substituted acrylonitriles in highly stereo-, regio-, and chemoselective manners. Lewis acid cocatalysts, such as AlMe3, AlMe2Cl, and BPh3, are found to promote the arylcyanation significantly. The cooperative catalysis of nickel and Lewis acid also allows the carbocyanation reaction using alkenyl and alkyl cy...

  1. Organobase-catalyzed three-component reactions for the synthesis of 4H-2-aminopyrans, condensed pyrans and polysubstituted benzenes


    Moustafa Sherief Moustafa; Saleh Mohammed Al-Mousawi; Maghraby Ali Selim; Ahmed Mohamed Mosallam; Mohamed Hilmy Elnagdi


    Novel routes for the preparation of 2-amino-4H-pyran-3-carbonitrile 9, amino-arylbenzoic acid ester derivatives 13a,b, 2-aminotetrahydro-4H-chromene-3-carbonitrile 18, 3-amino-4-cyanotetrahydronaphthalene-2-carboxylic acid ester 26 and 4-amino-3,5-dicyanophthalic acid ester derivatives 37a–c were developed. The synthetic methods utilize one-pot reactions of acetylene carboxylic acid esters, α,β-unsaturated nitriles and/or active methylenenitriles in the presence of L-proline or DABCO. Plausib...

  2. Metal ion roles and the movement of hydrogen during the reaction catalyzed by d-xylose isomerase: a joint X-ray and neutron diffraction study (United States)

    Kovalevsky, Andrey Y.; Hanson, Leif; Fisher, S. Zoe; Mustyakimov, Marat; Mason, Sax; Forsyth, Trevor; Blakeley, Matthew P.; Kean, David. A.; Wagner, Trixie; Carrell, H. L.; Katz, Amy K.; Glusker, Jenny P.; Langan, Paul


    SUMMARY Conversion of aldo to keto sugars by the metalloenzyme d-xylose isomerase (XI) is a multi-step reaction involving hydrogen transfer. We have determined the structure of this enzyme by neutron diffraction in order to locate H atoms (or their isotope D). Two studies are presented, one of XI containing cadmium and cyclic d-glucose (before sugar ring opening has occurred), and the other containing nickel and linear d-glucose (after ring opening has occurred but before isomerization). Previously we reported the neutron structures of ligand-free enzyme and enzyme with bound product. Data show that His54 is doubly protonated on the ring N in all four structures. Lys289 is neutral before ring opening, and gains a proton after this, the catalytic metal-bound water is deprotonated to hydroxyl during isomerization and O5 is deprotonated. These results lead to new suggestions as to how changes might take place over the course of the reaction. PMID:20541506

  3. Spectroscopic determination of hydrogenation rates and intermediates during carbonyl hydrogenation catalyzed by Shvo's hydroxycyclopentadienyl diruthenium hydride agrees with kinetic modeling based on independently measured rates of elementary reactions. (United States)

    Casey, Charles P; Beetner, Sharon E; Johnson, Jeffrey B


    The catalytic hydrogenation of benzaldehyde and acetophenone with the Shvo hydrogenation catalysts were monitored by in situ IR spectroscopy in both toluene and THF. The disappearance of organic carbonyl compound and the concentrations of the ruthenium species present throughout the hydrogenation reaction were observed. The dependence of the hydrogenation rate on substrate, H2 pressure, total ruthenium concentration, and solvent were measured. In toluene, bridging diruthenium hydride 1 was the only observable ruthenium species until nearly all of the substrate was consumed. In THF, both 1 and some monoruthenium hydride 2 were observed during the course of the hydrogenation. A full kinetic model of the hydrogenation based on rate constants for individual steps in the catalysis was developed. This kinetic model simulates the rate of carbonyl compound hydrogenation and of the amounts of ruthenium species 1 and 2 present during hydrogenations.

  4. Transient kinetics of heparin-catalyzed protease inactivation by antithrombin III. Characterization of assembly, product formation, and heparin dissociation steps in the factor Xa reaction. (United States)

    Craig, P A; Olson, S T; Shore, J D


    The kinetics of alpha-factor Xa inhibition by antithrombin III (AT) were studied in the absence and presence of heparin (H) with high affinity for antithrombin by stopped-flow fluorometry at I 0.3, pH 7.4 and 25 degrees C, using the fluorescence probe p-aminobenzamidine (P) and intrinsic protein fluorescence to monitor the reactions. Active site binding of p-aminobenzamidine to factor Xa was characterized by a 200-fold enhancement and 4-nm blue shift of the probe fluorescence emission spectrum (lambda max 372 nm), 29-nm red shift of the excitation spectrum (lambda max 322 nm), and dissociation constant (KD) of about 80 microM. Under pseudo-first order conditions [( AT]0, [H]0, [P]0 much greater than [Xa]0), the observed factor Xa inactivation rate constant (kobs) measured by p-aminobenzamidine displacement or residual enzymatic activity increased linearly with the "effective" antithrombin concentration (i.e. corrected for probe competition) up to 300 microM in the absence of heparin, indicating a simple bimolecular process with a rate constant of 2.1 x 10(3) M-1 s-1. In the presence of heparin, a similar linear dependence of kobs on effective AT.H complex concentration was found up to 25 microM whether the reaction was followed by probe displacement or the quenching of AT.H complex protein fluorescence due to heparin dissociation, consistent with a bimolecular reaction between AT.H complex and free factor Xa with a 300-fold enhanced rate constant of 7 x 10(5) M-1 s-1. Above 25 microM AT.H complex, an increasing dead time displacement of p-aminobenzamidine and a downward deviation of kobs from the initial linear dependence on AT.H complex concentration were found, reflecting the saturation of an intermediate Xa.AT.H complex with a KD of 200 microM and a limiting rate of Xa-AT product complex formation of 140 s-1. Kinetic studies at catalytic heparin concentrations yielded a kcat/Km for factor Xa at saturating antithrombin of 7 x 10(5) M-1 s-1 in agreement with the

  5. A valence bond modeling of trends in hydrogen abstraction barriers and transition states of hydroxylation reactions catalyzed by cytochrome P450 enzymes. (United States)

    Shaik, Sason; Kumar, Devesh; de Visser, Sam P


    The paper outlines the fundamental factors that govern the mechanisms of alkane hydroxylation by cytochrome P450 and the corresponding barrier heights during the hydrogen abstraction and radical rebound steps of the process. This is done by a combination of density functional theory calculations for 11 alkanes and valence bond (VB) modeling of the results. The energy profiles and transition states for the various steps are reconstructed using VB diagrams (Shaik, S. S. J. Am. Chem. Soc. 1981, 103, 3692-3701. Shaik, S.; Shurki, A. Angew. Chem. Int. Ed. 1999, 38, 586-625.) and the DFT barriers are reproduced by the VB model from raw data based on C-H bond energies. The model explains a variety of other features of P450 hydroxylations: (a) the nature of the polar effect during hydrogen abstraction, (b) the difference between the activation mechanisms leading to the Fe(IV) vs the Fe(III) electromers, (c) the difference between the gas phase and the enzymatic reaction, and (d) the dependence of the rebound barrier on the spin state. The VB mechanism shows that the active species of the enzyme performs a complex reaction that involves multiple bond making and breakage mechanisms by utilizing an intermediate VB structure that cuts through the high barrier of the principal transformation between reactants and products, thereby mediating the process at a low energy cost. The correlations derived in this paper create order and organize the data for a process of a complex and important enzyme. This treatment can be generalized to the reactivity patterns of nonheme systems and synthetic iron-oxo porphyrin reagents.

  6. Micro/milliflow processing with selective catalyst microwave heating in the Cu-catalyzed Ullmann etherification reaction: a μ(2)-process. (United States)

    Benaskar, Faysal; Patil, Narendra G; Rebrov, Evgeny V; Ben-Abdelmoumen, Alladin; Meuldijk, Jan; Hulshof, Lumbertus A; Hessel, Volker; Schouten, Jaap C


    A μ(2)-process in the Ullmann-type C-O coupling of potassium phenolate and 4-chloropyridine was successfully performed in a combined microwave (MW) and microflow process. Selective MW absorption in a micro-fixed-bed reactor (μ-FBR) by using a supported Cu nanocatalyst resulted in an increased activity compared to an oil-bath heated process. Yields of up to 80 % were attained by using a multisegmented μ-FBR without significant catalyst deactivation. The μ-FBR was packed with beads coated with Cu/TiO(2) and CuZn/TiO(2) catalysts. Temperature measurements along axial positions of the reactor were performed by using a fiber-optic probe in the catalyst bed. The simultaneous application of MW power and temperature sensors resulted in an isothermal reactor at 20 W. Initially, only solvent was used to adjust the MW field density in the cavity and optimize the power utility. Subsequently, the reaction mixture was added to ensure the maximum MW power transfer by adjusting the waveguide stub tuners to steady-state operations as a result of the changed reaction mixture composition and, therefore, the dielectric properties. Finally, the beneficial influence of the Cu/TiO(2)- and CuZn/TiO(2)-coated glass beads (200 μm) on the MW absorption as a result of the additional absorbing effect of the metallic Cu nanoparticles was optimized in a fine-tuning step. For the catalyst synthesis, various sol-gel, deposition, and impregnation methods provided Cu catalyst loadings of around 1 wt %. The addition of Zn to the Cu nanocatalyst revealed an increased catalyst activity owing to the presence of stable Cu(0). Multilaminar mixing was necessary because of the large difference in fluid viscosities. To the best of our knowledge, this work is the first extended experimental survey of the decisive parameters to combine microprocess and single-mode MW technology following the concepts of "novel process windows" for organic syntheses. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGa

  7. Density functional theory study of the reaction mechanism for competitive carbon-hydrogen and carbon-halogen bond activations catalyzed by transition metal complexes. (United States)

    Yang, Xinzheng; Hall, Michael B


    Carbon-hydrogen and carbon-halogen bond activations between halobenzenes and metal centers were studied by density functional theory with the nonempirical meta-GGA Tao-Perdew-Staroverov-Scuseria functional and an all-electron correlation-consistent polarized valence double-zeta basis set. Our calculations demonstrate that the hydrogen on the metal center and halogen in halobenzene could exchange directly through a kite-shaped transition state. Transition states with this structure were previously predicted to have high energy barriers (J. Am. Chem. Soc. 2005, 127, 279), and this prediction misled others in proposing a mechanism for their recent experimental study (J. Am. Chem. Soc. 2006, 128, 3303). Furthermore, other halo-carbon activation pathways were found in the detailed mechanism for the competitive reactions between cationic titanium hydride complex [Cp*((t)Bu(3)P=N)TiH](+) and chlorobenzene under different pressure of H(2). These pathways include the ortho-C-H and Ti-H bond activations for the formation and release of H(2) and the indirect C-Cl bond activation via beta-halogen elimination for the movement of the C(6)H(4) ring and the formation of a C-N bond in the observed final product. A new stable isomer of the observed product with a similar total energy and an unexpected bridging between the Cp* ring and the metal center by a phenyl ring is also predicted.

  8. Role of Ser-257 in the sliding mechanism of NADP(H) in the reaction catalyzed by the Aspergillus fumigatus flavin-dependent ornithine N5-monooxygenase SidA. (United States)

    Shirey, Carolyn; Badieyan, Somayesadat; Sobrado, Pablo


    SidA (siderophore A) is a flavin-dependent N-hydroxylating monooxygenase that is essential for virulence in Aspergillus fumigatus. SidA catalyzes the NADPH- and oxygen-dependent formation of N(5)-hydroxyornithine. In this reaction, NADPH reduces the flavin, and the resulting NADP(+) is the last product to be released. The presence of NADP(+) is essential for activity, as it is required for stabilization of the C4a-hydroperoxyflavin, which is the hydroxylating species. As part of our efforts to determine the molecular details of the role of NADP(H) in catalysis, we targeted Ser-257 for site-directed mutagenesis and performed extensive characterization of the S257A enzyme. Using a combination of steady-state and stopped-flow kinetic experiments, substrate analogs, and primary kinetic isotope effects, we show that the interaction between Ser-257 and NADP(H) is essential for stabilization of the C4a-hydroperoxyflavin. Molecular dynamics simulation results suggest that Ser-257 functions as a pivot point, allowing the nicotinamide of NADP(+) to slide into position for stabilization of the C4a-hydroperoxyflavin.

  9. The Effect of WO3 Modification of ZrO2 Support on the Ni-Catalyzed Dry Reforming of Biogas Reaction for Syngas Production

    Directory of Open Access Journals (Sweden)

    Nikolaos D. Charisiou


    Full Text Available The time-on-stream catalytic performance and stability of 8 wt. % Ni catalyst supported on two commercially available catalytic supports, ZrO2 and 15 wt.% WO3-ZrO2, was investigated under the biogas dry reforming reaction for syngas production, at 750°C and a biogas quality equal to CH4/CO2 = 1.5, that represents a common concentration of real biogas. A number of analytical techniques such as N2 adsorption/desorption (BET method, XRD, H2-TPR, NH3- and CO2-TPD, SEM, ICP, thermal analysis (TGA/DTG and Raman spectroscopy were used in order to determine textural, structural and other physicochemical properties of the catalytic materials, and the type of carbon deposited on the catalytic surface of spent samples. These techniques were used in an attempt to understand better the effects of WO3-induced modifications on the catalyst morphology, physicochemical properties and catalytic performance. Although Ni dispersion and reducibility characteristics were found superior on the modified Ni/WZr sample than that on Ni/Zr, its dry reforming of methane (DRM performance was inferior; a result attributed to the enhanced acidity and complete loss of the basicity recorded on this catalyst, an effect that competes and finally overshadows the benefits of the other superior properties. Raman studies revealed that the degree of graphitization decreases with the insertion of WO3 in the crystalline structure of the ZrO2 support, as the ID/IG peak intensity ratio is 1.03 for the Ni/Zr and 1.29 for the Ni/WZr catalyst.

  10. Substituted tridentate pyrazolyl ligands for chromium and nickel-catalyzed ethylene oligomerization reactions: effect of auxiliary ligand on activity and selectivity

    Energy Technology Data Exchange (ETDEWEB)

    Oliveira, Lucilene L. de; Campedelli, Roberta R.; Bergamo, Adao L.; Santos, Ana H.D.P dos; Casagrande, Osvaldo L., E-mail: osvaldo.casagrande@ufrgs.b [Universidade Federal do Rio Grande do Sul (UFRGS), Porto Alegre, RS (Brazil). Inst. de Quimica. Lab. de Catalise Molecular


    Two new chromium(III) complexes [CrCl{sub 3}(L)] based on tridentate ligands (1a, L = bis[2-(3-phenyl-1-pyrazolyl)ethyl)]amine; 2a, L bis[2-(3-methyl-5-phenyl-l-pyrazolyl)ethyl]sulfide) have been prepared and characterized by elemental analysis. Upon activation with methylaluminoxane (MAO), these pre-catalysts showed high turnover frequencies for ethylene oligomerization under optimized conditions (TOFs = 22.9-36.4 x 103 mol C{sub 2}H{sub 4} (mol Cr{sup III}){sup -1} h{sup -1}, [Cr] = 10.0 mumol, 80 deg C, 20 bar ethylene, MAO: Cr = 300, oligomerization time = 20 min), producing alpha-olefins in the range C{sub 4}-C{sub 14+} with high selectively (67.71-73.47%). The catalytic performances are substantially affected by the ligand environment, especially the substituents at the 3- and 5-positions of the pyrazolyl rings. In parallel, the use of nickel complexes such as NiCl{sub 2}{l_brace}bis[2-(3,5-dimethyl-1-pyrazolyl)methyl]benzylamine{r_brace} (3) and NiCl{sub 2}{l_brace}bis[2-(3,5-dimethyl-1-pyrazolyl)ethyl)]ether{r_brace} (5) in oligomerization reactions carried out in the presence of triphenylphosphine (PPh{sub 3}) afforded highly active catalytic systems with turnover frequencies (TOFs) varying from 36.4 to 154.2 x 10{sup 3} mol C{sub 2}H{sub 4} (mol Ni{sup II}){sup -1} h{sup -1}. The presence of this auxiliary ligand has a strong impact on the selectivity towards the production of a-olefins, decreasing substantially the amount of 1-butene with a concomitant increase of the 2-butene fractions. Attempts to crystallize the nickel complex 3 afforded the tetrametallic [{l_brace} (L)(mu{sub 3}-Cl)NiCl{r_brace}{sub 4}] (4, L 1-anilinomethyl-3,5-dimethylpyrazole) which was characterized by X-ray diffraction analysis. (author)

  11. The Vanadium Iodoperoxidase from the marine flavobacteriaceae species Zobellia galactanivorans reveals novel molecular and evolutionary features of halide specificity in the vanadium haloperoxidase enzyme family. (United States)

    Fournier, Jean-Baptiste; Rebuffet, Etienne; Delage, Ludovic; Grijol, Romain; Meslet-Cladière, Laurence; Rzonca, Justyna; Potin, Philippe; Michel, Gurvan; Czjzek, Mirjam; Leblanc, Catherine


    Vanadium haloperoxidases (VHPO) are key enzymes that oxidize halides and are involved in the biosynthesis of organo-halogens. Until now, only chloroperoxidases (VCPO) and bromoperoxidases (VBPO) have been characterized structurally, mainly from eukaryotic species. Three putative VHPO genes were predicted in the genome of the flavobacterium Zobellia galactanivorans, a marine bacterium associated with macroalgae. In a phylogenetic analysis, these putative bacterial VHPO were closely related to other VHPO from diverse bacterial phyla but clustered independently from eukaryotic algal VBPO and fungal VCPO. Two of these bacterial VHPO, heterogeneously produced in Escherichia coli, were found to be strictly specific for iodide oxidation. The crystal structure of one of these vanadium-dependent iodoperoxidases, Zg-VIPO1, was solved by multiwavelength anomalous diffraction at 1.8 Å, revealing a monomeric structure mainly folded into α-helices. This three-dimensional structure is relatively similar to those of VCPO of the fungus Curvularia inaequalis and of Streptomyces sp. and is superimposable onto the dimeric structure of algal VBPO. Surprisingly, the vanadate binding site of Zg-VIPO1 is strictly conserved with the fungal VCPO active site. Using site-directed mutagenesis, we showed that specific amino acids and the associated hydrogen bonding network around the vanadate center are essential for the catalytic properties and also the iodide specificity of Zg-VIPO1. Altogether, phylogeny and structure-function data support the finding that iodoperoxidase activities evolved independently in bacterial and algal lineages, and this sheds light on the evolution of the VHPO enzyme family. Copyright © 2014, American Society for Microbiology. All Rights Reserved.

  12. Enyne Metathesis Catalyzed by Ruthenium Carbene Complexes

    DEFF Research Database (Denmark)

    Poulsen, Carina Storm; Madsen, Robert


    Enyne metathesis combines an alkene and an alkyne into a 1,3-diene. The first enyne metathesis reaction catalyzed by a ruthenium carbene complex was reported in 1994. This review covers the advances in this transformation during the last eight years with particular emphasis on methodology...

  13. Enzyme-Catalyzed Transetherification of Alkoxysilanes

    Directory of Open Access Journals (Sweden)

    Peter G. Taylor


    Full Text Available We report the first evidence of an enzyme-catalyzed transetherification of model alkoxysilanes. During an extensive enzymatic screening in the search for new biocatalysts for silicon-oxygen bond formation, we found that certain enzymes promoted the transetherification of alkoxysilanes when tert-butanol or 1-octanol were used as the reaction solvents.

  14. Exploring possible reaction pathways for the o-atom transfer reactions to unsaturated substrates catalyzed by a [Ni-NO2] ↔ [Ni-NO] redox couple using DFT methods. (United States)

    Tsipis, Athanassios C


    The (nitro)(N-methyldithiocarbamato)(trimethylphospane)nickel(II), [Ni(NO 2 )(S 2 CNHMe)(PMe 3 )] complex catalyses efficiently the O-atom transfer reactions to CO and acetylene. Energetically feasible sequence of elementary steps involved in the catalytic cycle of the air oxidation of CO and acetylene are proposed promoted by the Ni(NO 2 )(S 2 CNHMe)(PMe 3 )] ↔ Ni(NO 2 )(S 2 CNHMe)(PMe 3 ) redox couple using DFT methods both in vacuum and dichloromethane solutions. The catalytic air oxidation of HC≡CH involves formation of a five-member metallacycle intermediate, via a [3 + 2] cyclo-addition reaction of HC≡CH to the Ni-N = O moiety of the Ni(NO 2 )(S 2 CNHMe)(PMe 3 )] complex, followed by a β H-atom migration toward the C α carbon atom of the coordinated acetylene and release of the oxidation product (ketene). The geometric and energetic reaction profile for the reversible [Ni( κN1-NO 2 )(S 2 CNHMe)(PMe 3 )] ⇌ [Ni( κO,O2-ONO)(S 2 CNHMe)(PMe 3 )] linkage isomerization has also been modeled by DFT calculations. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

  15. Platinum-Catalyzed Selective Tin-Carbon Bond Formation

    NARCIS (Netherlands)

    Thoonen, Sander Hendrikus Lambertus


    In conclusion, two improved methods for the selective synthesis of monoorganotin trihalides were developed. The platinum-catalyzed Kocheshkov redistribution reaction of dialkyltin dichlorides with tin tetrachloride is the most interesting. Contrary to the other two methods described (the direct

  16. Copper-Catalyzed Alkylation of Benzoxazoles with Secondary Alkyl Halides


    Ren P; Salihu I; Scopelliti R.; Hu XL


    Copper catalyzed direct alkylation of benzoxazoles using nonactivated secondary alkyl halides has been developed. The best catalyst is a new copper(I) complex (1) and the reactions are promoted by bis[2 (NN dimethylamino)ethyl] ether.

  17. Oxidations catalyzed by phenylacetone monooxygenase from Thermobifida fusca

    NARCIS (Netherlands)

    Gonzalo, Gonzalo de; Torres Pazmino, Daniel; Ottolina, Gianluca; Fraaije, Marco W.; Carrea, Giacomo


    Several organic sulfides, ketones and other organic systems have been tested as substrates in oxidation reactions catalyzed by the recently discovered phenylacetone monooxygenase from Thermobifida fusca. The biocatalytic properties of this Baeyer–Villiger monooxygenase have been studied, revealing

  18. Catalyzing RE Project Development

    Energy Technology Data Exchange (ETDEWEB)

    Anderson, Kate; Elgqvist, Emma; Walker, Andy; Cutler, Dylan; Olis, Dan; DiOrio, Nick; Simpkins, Travis


    This poster details how screenings done with REopt - NREL's software modeling platform for energy systems integration and optimization - are helping to catalyze the development of hundreds of megawatts of renewable energy.

  19. On the regiospecificity of vanadium bromoperoxidase. (United States)

    Martinez, J S; Carroll, G L; Tschirret-Guth, R A; Altenhoff, G; Little, R D; Butler, A


    Vanadium haloperoxidase enzymes catalyze the oxidation of halide ions by hydrogen peroxide, producing an oxidized intermediate, which can halogenate an organic substrate or react with a second equivalent of hydrogen peroxide to produce dioxygen. Haloperoxidases are thought to be involved in the biogenesis of halogenated natural products isolated from marine organisms, including indoles and terpenes, of which many are selectively oxidized or halogenated. Little has been shown concerning the ability of the marine haloperoxidases to catalyze regioselective reactions. Here we report the regiospecific bromoperoxidative oxidation of 1,3-di-tert-butylindole by V-BrPO from the marine algae Ascophyllum nodosum and Corallina officinalis. Both enzymes catalyze the regiospecific oxidation of 1,3-di-tert-butylindole in a reaction requiring both H(2)O(2) and Br(-) as substrates, but which produce the unbrominated 1,3-di-tert-butyl-2-indolinone product exclusively, in near quantitative yield (i.e. one H(2)O(2) consumed per product). By contrast, reactions with the controlled addition of aqueous bromine solution (HOBr = Br(2) = Br(3)(-)) produce three monobromo and one dibromo-2-indolinone products, all of which differ from the V-BrPO-catalyzed product. Further, reactivities of 1,3-di-tert-butyl-2-indolinone with both aqueous bromine and V-BrPO differ significantly and shed light onto the possible nature of the oxidizing intermediate. This is the first example of a regiospecific bromination by a vanadium haloperoxidase and further extends their usefulness as catalysts.

  20. Ligand intermediates in metal-catalyzed reactions

    Energy Technology Data Exchange (ETDEWEB)

    Gladysz, J.A.


    This report consists of six sections, which cover pi/sigma equilibria in aldehyde and ketone complexes, abstraction of vinylic protons from alkene complexes, mechanism of rearrangement of alkylidene to alkene complexes, rearrangement of terminal acetylene to vinylidene complexes, synthesis and reactivity of lithiocarbide complexes, and new catalysts for the epimerization of secondary alcohols; carbon-hydrogen bond activation in alkoxide complexes. (WET)

  1. Glicerólise de óleo de peixe catalisada por lipase comercial de Rhizomucor miehei em meio com surfactante de grau alimentício Glycerolysis of fish oil catalyzed by a commercial lipase from Rhizomucor miehei in reaction media containing food grade surfactant

    Directory of Open Access Journals (Sweden)

    Joanna Silva Santos


    Full Text Available Omega-3 enriched partial acylglycerols are beneficial for human health. The aim of this study was to obtain monoacylglycerols (MAG and diacylglycerols (DAG by means of glycerolysis of fish oil catalyzed by a lipase from Rhizomucor miehei in the presence of food grade surfactants (Tween 65, 80 or 85. Glycerolysis was successful in the reaction media for all the tested surfactants, showing their potential for use as additives in such a system. The best results, however, were obtained for the reaction medium in the absence of surfactant whose peroxide value was the lowest after glycerolysis.

  2. Biodiesel production by enzyme-catalyzed transesterification

    Directory of Open Access Journals (Sweden)

    Stamenković Olivera S.


    Full Text Available The principles and kinetics of biodiesel production from vegetable oils using lipase-catalyzed transesterification are reviewed. The most important operating factors affecting the reaction and the yield of alkyl esters, such as: the type and form of lipase, the type of alcohol, the presence of organic solvents, the content of water in the oil, temperature and the presence of glycerol are discussed. In order to estimate the prospects of lipase-catalyzed transesterification for industrial application, the factors which influence the kinetics of chemically-catalysed transesterification are also considered. The advantages of lipase-catalyzed transesterification compared to the chemically-catalysed reaction, are pointed out. The cost of down-processing and ecological problems are significantly reduced by applying lipases. It was also emphasized that lipase-catalysed transesterification should be greatly improved in order to make it commercially applicable. The further optimization of lipase-catalyzed transesterification should include studies on the development of new reactor systems with immobilized biocatalysts and the addition of alcohol in several portions, and the use of extra cellular lipases tolerant to organic solvents, intracellular lipases (i.e. whole microbial cells and genetically-modified microorganisms ("intelligent" yeasts.

  3. Gold-catalyzed naphthalene functionalization

    Directory of Open Access Journals (Sweden)

    Iván Rivilla


    Full Text Available The complexes IPrMCl (IPr = 1,3-bis(diisopropylphenylimidazol-2-ylidene, M = Cu, 1a; M = Au, 1b, in the presence of one equiv of NaBAr'4 (Ar' = 3,5-bis(trifluoromethylphenyl, catalyze the transfer of carbene groups: C(RCO2Et (R = H, Me from N2C(RCO2Et to afford products that depend on the nature of the metal center. The copper-based catalyst yields exclusively a cycloheptatriene derivative from the Buchner reaction, whereas the gold analog affords a mixture of products derived either from the formal insertion of the carbene unit into the aromatic C–H bond or from its addition to a double bond. In addition, no byproducts derived from carbene coupling were observed.

  4. Muon catalyzed fusion

    Energy Technology Data Exchange (ETDEWEB)

    Ishida, K. [Advanced Meson Science Laboratory, RIKEN, 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan); Nagamine, K. [Muon Science Laboratory, IMSS-KEK, 1-1 Oho, Tsukuba, Ibaraki 305-0801 (Japan); Matsuzaki, T. [Advanced Meson Science Laboratory, RIKEN, 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan); Kawamura, N. [Muon Science Laboratory, IMSS-KEK, 1-1 Oho, Tsukuba, Ibaraki 305-0801 (Japan)


    The latest progress of muon catalyzed fusion study at the RIKEN-RAL muon facility (and partly at TRIUMF) is reported. The topics covered are magnetic field effect, muon transfer to {sup 3}He in solid D/T and ortho-para effect in dd{mu} formation.

  5. A new strategy to construct a C=C-CF3 subunit via CuBr-catalyzed domino reaction of homopropargyl amines: an efficient synthesis of trifluoromethyl containing building blocks 4-trifluoromethyl-2,3-dihydro-pyrroliums. (United States)

    Ge, Guang-Cun; Huang, Xiao-Jun; Ding, Chang-Hua; Wan, Shi-Li; Dai, Li-Xin; Hou, Xue-Long


    A new strategy for the construction of a C=C-CF3 subunit has been developed via CuBr-catalyzed domino cyclization-trifluoromethylation of homopropargyl amines with Umemoto's reagent. 4-Trifluoromethyl-2,3-dihydro-pyrroliums were produced in high yields. The usefulness of these products has been demonstrated by the transformation of them into various other trifluoromethylated molecules.

  6. Hydrolysis of Toxic Natural Glucosides Catalyzed by Cyclodextrin Dicyanohydrins

    DEFF Research Database (Denmark)

    Bjerre, Jeannette; Nielsen, Erik Holm; Bols, Mikael


    The hydrolysis of toxic 7-hydroxycoumarin glucosides and other aryl and alkyl glucosides, catalyzed by modified a- and ß-cyclodextrin dicyanohydrins, was investigated using different UV, redox, or HPAEC detection assays. The catalyzed reactions all followed Michaelis-Menten kinetics, and an impre......The hydrolysis of toxic 7-hydroxycoumarin glucosides and other aryl and alkyl glucosides, catalyzed by modified a- and ß-cyclodextrin dicyanohydrins, was investigated using different UV, redox, or HPAEC detection assays. The catalyzed reactions all followed Michaelis-Menten kinetics...... degree of catalysis was also found for the toxic hydroxycoumarin esculin. A novel synthesized diaminomethyl ß-cyclodextrin showed a weak catalysis of p-nitrophenyl ß-D-glucopyranoside hydrolysis....

  7. CU(II): catalyzed hydrazine reduction of ferric nitrate

    Energy Technology Data Exchange (ETDEWEB)

    Karraker, D.G.


    A method is described for producing ferrous nitrate solutions by the cupric ion-catalyzed reduction of ferric nitrate with hydrazine. The reaction is complete in about 1.5 hours at 40/sup 0/C. Hydrazoic acid is also produced in substantial quantities as a reaction byproduct.

  8. Manganese-Catalyzed Aerobic Heterocoupling of Aryl Grignard Reagents

    DEFF Research Database (Denmark)

    Ghaleshahi, Hajar Golshahi; Antonacci, Giuseppe; Madsen, Robert


    An improved protocol has been developed for the MnCl2-catalyzed cross-coupling reaction of two arylmagnesium bromides under dioxygen. The reaction was achieved by using the Grignard reagents in a 2:1 ratio and 20 % of MnCl2. Very good yields of the heterocoupling product were obtained when the li...


    African Journals Online (AJOL)

    Sodium selenate efficiently catalyzes the three-component Biginelli reaction of an aldehyde, a,β-keto ester and urea or thiourea under solvent-free conditions to afford the corresponding 3,4-dihydropyrimidin-2(1H)-ones or –thiones in excellent yields. KEY WORDS: Dihydropyrimidinones, Sodium selenate, Biginelli reaction, ...

  10. Catalyzing alignment processes

    DEFF Research Database (Denmark)

    Lauridsen, Erik Hagelskjær; Jørgensen, Ulrik


    This paper describes how environmental management systems (EMS) spur the circulation of processes that support the constitution of environmental issues as specific environ¬mental objects and objectives. EMS catalyzes alignmentprocesses that produce coherence among the different elements involved...... time and in combination with other social processes establish more aligned and standardized environmental performance between countries. However, examples of the introduction of environmental management suggests that EMS’ only plays a minor role in developing the actual environmental objectives...

  11. Dual chemistry catalyzed by human acireductone dioxygenase. (United States)

    Deshpande, Aditi R; Pochapsky, Thomas C; Petsko, Gregory A; Ringe, Dagmar


    Acireductone dioxygenase (ARD) from the methionine salvage pathway of Klebsiella oxytoca is the only known naturally occurring metalloenzyme that catalyzes different reactions in vivo based solely on the identity of the divalent transition metal ion (Fe2+ or Ni2+) bound in the active site. The iron-containing isozyme catalyzes the cleavage of substrate 1,2-dihydroxy-3-keto-5-(thiomethyl)pent-1-ene (acireductone) by O2 to formate and the ketoacid precursor of methionine, whereas the nickel-containing isozyme uses the same substrates to catalyze an off-pathway shunt to form methylthiopropionate, carbon monoxide and formate. This dual chemistry was recently demonstrated in vitro by ARD from Mus musculus (MmARD), providing the first example of a mammalian ARD exhibiting metal-dependent catalysis. We now show that human ARD (HsARD) is also capable of metal-dependent dual chemistry. Recombinant HsARD was expressed and purified to obtain a homogeneous enzyme with a single transition metal ion bound. As with MmARD, the Fe2+-bound HsARD shows the highest activity and catalyzes on-pathway chemistry, whereas Ni2+, Co2+ or Mn2+ forms catalyze off-pathway chemistry. The thermal stability of the HsARD isozymes is a function of the metal ion identity, with Ni2+-bound HsARD being the most stable followed by Co2+ and Fe2+, and Mn2+-bound HsARD being the least stable. As with the bacterial ARD, solution NMR data suggest that HsARD isozymes can have significant structural differences depending upon the metal ion bound. © The Author 2017. Published by Oxford University Press. All rights reserved. For permissions, please e-mail:

  12. Imidazole catalyzes chlorination by unreactive primary chloramines. (United States)

    Roemeling, Margo D; Williams, Jared; Beckman, Joseph S; Hurst, James K


    Hypochlorous acid and simple chloramines (RNHCl) are stable biologically derived chlorinating agents. In general, the chlorination potential of HOCl is much greater than that of RNHCl, allowing it to oxidize or chlorinate a much wider variety of reaction partners. However, in this study we demonstrate by kinetic analysis that the reactivity of RNHCl can be dramatically promoted by imidazole and histidyl model compounds via intermediary formation of the corresponding imidazole chloramines. Two biologically relevant reactions were investigated--loss of imidazole-catalyzed chlorinating capacity and phenolic ring chlorination using fluorescein and the tyrosine analog, 4-hydroxyphenylacetic acid (HPA). HOCl reacted stoichiometrically with imidazole, N-acetylhistidine (NAH), or imidazoleacetic acid to generate the corresponding imidazole chloramines which subsequently decomposed. Chloramine (NH2Cl) also underwent a markedly accelerated loss in chlorinating capacity when NAH was present, although in this case N-α-acetylhistidine chloramine (NAHCl) did not accumulate, indicating that the catalytic intermediate must be highly reactive. Mixing HOCl with 1-methylimidazole (MeIm) led to very rapid loss in chlorinating capacity via formation of a highly reactive chlorinium ion (MeImCl(+)) intermediate; this behavior suggests that the reactive forms of the analogous imidazole chloramines are their conjugate acids, e.g., the imidazolechlorinium ion (HImCl(+)). HOCl-generated imidazole chloramine (ImCl) reacted rapidly with fluorescein in a specific acid-catalyzed second-order reaction to give 3'-monochloro and 3',5'-dichloro products. Equilibrium constants for the transchlorination reactions HOCl + HIm = H2O + ImCl and NH2Cl + HIm = NH3 + ImCl were estimated from the dependence of the rate constants on [HIm]/[HOCl] and literature data. Acid catalysis again suggests that the actual chlorinating agent is HImCl(+); consistent with this interpretation, MeIm markedly catalyzed

  13. Palladium-Catalyzed Modification of Unprotected Nucleosides, Nucleotides, and Oligonucleotides

    Directory of Open Access Journals (Sweden)

    Kevin H. Shaughnessy


    Full Text Available Synthetic modification of nucleoside structures provides access to molecules of interest as pharmaceuticals, biochemical probes, and models to study diseases. Covalent modification of the purine and pyrimidine bases is an important strategy for the synthesis of these adducts. Palladium-catalyzed cross-coupling is a powerful method to attach groups to the base heterocycles through the formation of new carbon-carbon and carbon-heteroatom bonds. In this review, approaches to palladium-catalyzed modification of unprotected nucleosides, nucleotides, and oligonucleotides are reviewed. Polar reaction media, such as water or polar aprotic solvents, allow reactions to be performed directly on the hydrophilic nucleosides and nucleotides without the need to use protecting groups. Homogeneous aqueous-phase coupling reactions catalyzed by palladium complexes of water-soluble ligands provide a general approach to the synthesis of modified nucleosides, nucleotides, and oligonucleotides.

  14. Catalyzed Ceramic Burner Material

    Energy Technology Data Exchange (ETDEWEB)

    Barnes, Amy S., Dr.


    Catalyzed combustion offers the advantages of increased fuel efficiency, decreased emissions (both NOx and CO), and an expanded operating range. These performance improvements are related to the ability of the catalyst to stabilize a flame at or within the burner media and to combust fuel at much lower temperatures. This technology has a diverse set of applications in industrial and commercial heating, including boilers for the paper, food and chemical industries. However, wide spread adoption of catalyzed combustion has been limited by the high cost of precious metals needed for the catalyst materials. The primary objective of this project was the development of an innovative catalyzed burner media for commercial and small industrial boiler applications that drastically reduce the unit cost of the catalyzed media without sacrificing the benefits associated with catalyzed combustion. The scope of this program was to identify both the optimum substrate material as well as the best performing catalyst construction to meet or exceed industry standards for durability, cost, energy efficiency, and emissions. It was anticipated that commercial implementation of this technology would result in significant energy savings and reduced emissions. Based on demonstrated achievements, there is a potential to reduce NOx emissions by 40,000 TPY and natural gas consumption by 8.9 TBtu in industries that heavily utilize natural gas for process heating. These industries include food manufacturing, polymer processing, and pulp and paper manufacturing. Initial evaluation of commercial solutions and upcoming EPA regulations suggests that small to midsized boilers in industrial and commercial markets could possibly see the greatest benefit from this technology. While out of scope for the current program, an extension of this technology could also be applied to catalytic oxidation for volatile organic compounds (VOCs). Considerable progress has been made over the course of the grant

  15. Heterogeneously-Catalyzed Conversion of Carbohydrates (United States)

    Vigier, Karine De Oliveira; Jérôme, François

    Polyfunctionality of carbohydrates and their low solubility in conventional organic solvents make rather complex their conversion to higher value added chemicals. Therefore, innovative processes are now strongly needed in order to increase the selectivity of these reactions. Here, we report an overview of the different heterogeneously-catalyzed processes described in the literature. In particular, hydrolysis, dehydration, oxidation, esterification, and etherification of carbohydrates are presented. We shall discuss the main structural parameters that need to be controlled and that permit the conversion of carbohydrates to bioproducts with good selectivity. The conversion of monosaccharides and disaccharides over solid catalysts, as well as recent advances in the heterogeneously-catalyzed conversion of cellulose, will be presented.

  16. Multicomponent reactions in polymer synthesis. (United States)

    Kakuchi, Ryohei


    More participants, yet efficient reactions: Multicomponent reactions (MCRs) have found application in polymer chemistry both in the synthesis of multifunctional monomers and in post-polymerization modification. Examples include the Passerini three-component reaction, the Ugi four-component reaction, and the copper-catalyzed MCR. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Kinetics of Bio-Reactions

    DEFF Research Database (Denmark)

    Villadsen, John


    his chapter predicts the specific rates of reaction by means of a mathematical expression, the kinetics of the reaction. This expression can be derived through a mechanistic interpretation of an enzymatically catalyzed reaction, but it is essentially of empirical nature for cell reactions. The mo...

  18. Structural basis for Diels-Alder ribozyme-catalyzed carbon-carbon bond formation (United States)

    Serganov, Alexander; Keiper, Sonja; Malinina, Lucy; Tereshko, Valentina; Skripkin, Eugene; Höbartner, Claudia; Polonskaia, Anna; Phan, Anh Tuân; Wombacher, Richard; Micura, Ronald; Dauter, Zbigniew; Jäschke, Andres; Patel, Dinshaw J


    The majority of structural efforts addressing RNA’s catalytic function have focused on natural ribozymes, which catalyze phosphodiester transfer reactions. By contrast, little is known about how RNA catalyzes other types of chemical reactions. We report here the crystal structures of a ribozyme that catalyzes enantioselective carbon-carbon bond formation by the Diels-Alder reaction in the unbound state and in complex with a reaction product. The RNA adopts a λ-shaped nested pseudoknot architecture whose preformed hydrophobic pocket is precisely complementary in shape to the reaction product. RNA folding and product binding are dictated by extensive stacking and hydrogen bonding, whereas stereoselection is governed by the shape of the catalytic pocket. Catalysis is apparently achieved by a combination of proximity, complementarity and electronic effects. We observe structural parallels in the independently evolved catalytic pocket architectures for ribozyme- and antibody-catalyzed Diels-Alder carbon-carbon bond-forming reactions. PMID:15723077

  19. Silver and gold nanocluster catalyzed reduction of methylene blue ...

    Indian Academy of Sciences (India)


    nanoparticles in micellar medium. The arsine has been generated in situ from sodium arsenate ... trolled use of arsenic containing pesticides, paints and pigments etc. Keeping an eye on this grave situation of ... levels using micelle catalyzed reaction (Pal et al 1998). The participation of silver or gold nanoparticle as catalyst.

  20. Asymmetric gold-catalyzed lactonizations in water at room temperature** (United States)

    Handa, Sachin; Lippincott, Daniel J.; Slack, Eric D.; Aue, Donald H.


    Asymmetric gold-catalyzed hydrocarboxylations are reported that show broad substrate scope. The hydrophobic effect associated with in situ-formed aqueous nanomicelles leads to good-to-excellent ee’s of product lactones. In-flask product isolation, along with recycling of the catalyst and reaction medium, combine to arrive at an especially environmentally friendly process. PMID:25124085

  1. Palladium-catalyzed selective acyloxylation using sodium perborate as oxidant. (United States)

    Pilarski, Lukasz T; Janson, Pär G; Szabó, Kálmán J


    Sodium perborate (SPB), a principal component of washing powders, was employed as an inexpensive and eco-friendly oxidant in the palladium-catalyzed C-H acyloxylation of alkenes in excellent regio- and stereochemistry. The reactions used anhydrides as acyloxy sources. The method applies to both terminal and internal alkenes, and even benzylic C-H oxidation.

  2. Transition Metal Catalyzed Synthesis of Carboxylic Acids, Imines, and Biaryls

    DEFF Research Database (Denmark)

    Santilli, Carola; Madsen, Robert

    Dehydrogenative synthesis of carboxylic acids catalyzed by a ruthenium N- heterocycliccarbene complex. A new methodology for the synthesis of carboxylic acids from primary alcohols and hydroxide has been developed. The reaction is catalyzed by the ruthenium N-heterocycliccarbene complex [RuCl2(Ii......Pr)(p-cymene)] where dihydrogen is generated as the only by-product (Scheme i). The dehydrogenative reaction is performed in toluene, which allows for a simple isolation of the products by precipitation followed by extraction. Various substituted benzyl alcohols smoothly undergo the transformation. The fast conversion...... to the carboxylic acids can be explained by the involvement of a competing Cannizzaro reaction. The scope of the dehydrogenation was further extended to linear and branched saturated aliphatic alcohols, although longer reaction times are necessary to ensure complete substrate conversions. The kinetic isotope effect...

  3. Manganese Catalyzed C–H Halogenation

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Wei; Groves, John T.


    The remarkable aliphatic C–H hydroxylations catalyzed by the heme-containing enzyme, cytochrome P450, have attracted sustained attention for more than four decades. The effectiveness of P450 enzymes as highly selective biocatalysts for a wide range of oxygenation reactions of complex substrates has driven chemists to develop synthetic metalloporphyrin model compounds that mimic P450 reactivity. Among various known metalloporphyrins, manganese derivatives have received considerable attention since they have been shown to be versatile and powerful mediators for alkane hydroxylation and olefin epoxidation. Mechanistic studies have shown that the key intermediates of the manganese porphyrin-catalyzed oxygenation reactions include oxo- and dioxomanganese(V) species that transfer an oxygen atom to the substrate through a hydrogen abstraction/oxygen recombination pathway known as the oxygen rebound mechanism. Application of manganese porphyrins has been largely restricted to catalysis of oxygenation reactions until recently, however, due to ultrafast oxygen transfer rates. In this Account, we discuss recently developed carbon–halogen bond formation, including fluorination reactions catalyzed by manganese porphyrins and related salen species. We found that biphasic sodium hypochlorite/manganese porphyrin systems can efficiently and selectively convert even unactivated aliphatic C–H bonds to C–Cl bonds. An understanding of this novel reactivity derived from results obtained for the oxidation of the mechanistically diagnostic substrate and radical clock, norcarane. Significantly, the oxygen rebound rate in Mn-mediated hydroxylation is highly correlated with the nature of the trans-axial ligands bound to the manganese center (L–MnV$=$O). Based on the ability of fluoride ion to decelerate the oxygen rebound step, we envisaged that a relatively long-lived substrate radical could be trapped by a Mn–F fluorine source, effecting carbon–fluorine bond

  4. Medium effect on cyclohexene hydrocarbomethoxylation catalyzed by ruthenium (III) chloride


    Sevostyanova N.; Batashev S.


    This paper presents influence of some solvents on cyclohexene hydrocarbomethoxylation catalyzed by ruthenium(III) chloride. The objective of the work was contained in the determination of medium influence on the reaction rate and yield of product — methyl cyclohexanecarboxylate. The kinetic method was used as the main method of investigation. The gas–liquid chromatography method was used to analyze the reaction mass. Influence of methanol, toluene, acetone and water on the hydrocarmothoxy...

  5. on the elementary steps of acid zeolite catalyzed amination of light alcohols

    NARCIS (Netherlands)

    Veefkind, V.A.; Lercher, J.A.


    Potential elementary reaction steps in solid acid catalyzed amination of light alcohols are critically compared using hydrogen mordenite as (model) catalyst and the open mechanistic questions have been addressed. Transient kinetic experiments combined with in situ infrared spectroscopy and isotopic

  6. Triflic acid catalyzed oxidative lactonization and diacetoxylation of alkenes using peroxyacids as oxidants. (United States)

    Kang, Yan-Biao; Gade, Lutz H


    A clean and efficient diacetoxylation reaction of alkenes catalyzed by triflic acid using commercially available peroxyacids as the oxidants has been developed. This method was also applied in oxidative lactonizations of unsaturated carboxylic acids in good to high yields.

  7. Asymmetric H-D exchange reactions of fluorinated aromatic ketones

    KAUST Repository

    Zhao, Yujun


    Chiral bicyclic guanidine catalyzes the asymmetric H-D exchange reactions. Up to 30% ee was achieved. DFT calculations were employed to elucidate and explain the origin of the reaction\\'s stereoselectivity. © 2012 The Royal Society of Chemistry.

  8. Gold-Catalyzed Cyclizations of Alkynol-Based Compounds: Synthesis of Natural Products and Derivatives

    Directory of Open Access Journals (Sweden)

    Pedro Almendros


    Full Text Available The last decade has witnessed dramatic growth in the number of reactions catalyzed by gold complexes because of their powerful soft Lewis acid nature. In particular, the gold-catalyzed activation of propargylic compounds has progressively emerged in recent years. Some of these gold-catalyzed reactions in alkynes have been optimized and show significant utility in organic synthesis. Thus, apart from significant methodology work, in the meantime gold-catalyzed cyclizations in alkynol derivatives have become an efficient tool in total synthesis. However, there is a lack of specific review articles covering the joined importance of both gold salts and alkynol-based compounds for the synthesis of natural products and derivatives. The aim of this Review is to survey the chemistry of alkynol derivatives under gold-catalyzed cyclization conditions and its utility in total synthesis, concentrating on the advances that have been made in the last decade, and in particular in the last quinquennium.

  9. Synthesis of highly substituted pyrroles via a multimetal-catalyzed rearrangement-condensation-cyclization domino approach. (United States)

    Binder, Jörg T; Kirsch, Stefan F


    [reaction: see text] In a convenient one-pot process, easily accessed propargyl vinyl ethers and aromatic amines are effectively converted into tetra- and pentasubstituted 5-methylpyrroles which can further be transformed into 5-formylpyrroles via IBX-mediated oxidation. The cascade reaction proceeds through a silver(I)-catalyzed propargyl-Claisen rearrangement, an amine condensation, and a gold(I)-catalyzed 5-exo-dig heterocyclization.

  10. New Palladium-Catalyzed Approaches to Heterocycles and Carbocycles

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Qinhua [Iowa State Univ., Ames, IA (United States)


    The tert-butylimines of o-(1-alkynyl)benzaldehydes and analogous pyridinecarbaldehydes have been cyclized under very mild reaction conditions in the presence of I2, ICl, PhSeCl, PhSCl and p-O2NC6H4SCl to give the corresponding halogen-, selenium- and sulfur-containing disubstituted isoquinolines and naphthyridines, respectively. Monosubstituted isoquinolines and naphthyridines have been synthesized by the metal-catalyzed ring closure of these same iminoalkynes. This methodology accommodates a variety of iminoalkynes and affords the anticipated heterocycles in moderate to excellent yields. The Pd(II)-catalyzed cyclization of 2-(1-alkynyl)arylaldimines in the presence of various alkenes provides an efficient way to synthesize a variety of 4-(1-alkenyl)-3-arylisoquinolines in moderate to excellent yields. The introduction of an ortho-methoxy group on the arylaldimine promotes the Pd-catalyzed cyclization and stabilizes the resulting Pd(II) intermediate, improving the yields of the isoquinoline products. Highly substituted naphthalenes have been synthesized by the palladium-catalyzed annulation of a variety of internal alkynes, in which two new carbon-carbon bonds are formed in a single step under relatively mild reaction conditions. This method has also been used to synthesize carbazoles, although a higher reaction temperature is necessary. The process involves arylpalladation of the alkyne, followed by intramolecular Heck olefination and double bond isomerization. This method accommodates a variety of functional groups and affords the anticipated highly substituted naphthalenes and carbazoles in good to excellent yields. Novel palladium migratiodarylation methodology for the synthesis of complex fused polycycles has been developed, in which one or more sequential Pd-catalyzed intramolecular migration processes involving C-H activation are employed. The chemistry works best with electron-rich aromatics, which is in agreement

  11. Diels-Alder reactions catalyzed by derivated by mentholxyaluminium derivates supported on alumina and silica gel; Reacciones de Diels-Alder asimetrica catalizadas por derivados de mentoxialuminio soportados sobre alumina y gel de silice

    Energy Technology Data Exchange (ETDEWEB)

    Cativiela, C.; Garcia, J.L.; Mayoral, J.A.; Pires, E.; Rojo, A.J. [Departamento de Quimica Organica, Universidad de Zaragoza, Zaragoza (Spain)


    The solids obtained by treatment of alumina and, specially, silica gel with A1C1Et{sub 2} are efficient catalysts for Diels-Alder reactions. A similar methodology has been used to support menthoxyaluminium derivatives. The introduction of (-)-menthol reduces the catalytic activity, but these solids are able to promote the reaction between methacrolein and cyclopentadiene, leading to a moderate asymmetric induction. Both reaction rate and enantioselectivity are greatly influenced by the amount of (-)-menthol used to prepare the catalyst. So, solids obtained from equimolecular amounts of (-)-menthol and diethyl aluminium chloride lead to higher percentages of enantiomeric excess, but they have worse catalytic activity. Silica-supported catalysts are again more active than alumina-supported ones.

  12. Synthesis of Pyridobenzazepines Using a One-Pot Rh/Pd-Catalyzed Process. (United States)

    Lam, Heather; Tsoung, Jennifer; Lautens, Mark


    In recent years, our group has been developing multicatalytic reactions for the synthesis of biologically relevant heterocyclic compounds. An efficient dual-metal catalyzed reaction of electron-deficient o-chlorovinylpyridines with o-aminophenylboronic esters to access pyridobenzazepines is described. Combining a RhI-catalyzed arylation followed by a Pd0-catalyzed C-N coupling, in a one-pot procedure, provides a simplified method to access heterocycles without workup and purification after each step. The substrate scope encompasses a variety of N-H and N-alkylated pyridobenzazepine variants with yields up to 93%.

  13. Kinetic Parameters for the Noncatalyzed and Enzyme-Catalyzed Mutarotation of Glucose Using a Blood Glucometer (United States)

    Hardee, John R.; Delgado, Bryan; Jones, Wray


    The kinetic parameters for the conversion of alpha-D-glucose to beta-D-glucose were measured using a blood glucometer. The reaction order, rate constant, and Arrhenius activation energy are reported for the noncatalyzed reaction and turnover number and Michaelis constant are reported for the reaction catalyzed by porcine kidney mutarotase. The…

  14. DNA Self-assembly Catalyzed by Artificial Agents. (United States)

    Shi, Chao; Wang, Yifan; Zhang, Menghua; Ma, Cuiping


    Nucleic acids have been shown to be versatile molecules and engineered to produce various nanostructures. However, the poor rate of these uncatalyzed nucleic acid reactions has restricted the development and applications. Herein, we reported a novel finding that DNA self-assembly could be nonenzymatically catalyzed by artificial agents with an increasing dissociation rate constant K2. The catalytic role of several artificial agents in DNA self-assembly was verified by real-time fluorescent detection or agarose gel electrophoresis. We found that 20% PEG 200 could significantly catalyze DNA self-assembly and increase the reaction efficiency, such as linear hybridization chain reaction (HCR) and exponential hairpin assembly (EHA). Therefore, we foresee that a fast and efficient DNA self-assembly in structural DNA nanotechnology will be desirable.

  15. A DFT/B3LYP study of the mechanisms of the O2 formation reaction catalyzed by the [(terpy)(H2O)Mn(III)(O)2Mn(IV)(OH2)(terpy)](NO3)3 complex: A paradigm for photosystem II. (United States)

    Sproviero, Eduardo M


    We present a theoretical study of the reaction pathway for dioxygen molecular formation catalyzed by the [(terpy)(H2O)Mn(III)(O)2Mn(IV)(OH2) (terpy)](NO3)3 (terpy=2,2':6',2″-terpyridine) complex based on DFT-B3LYP calculations. In the initial state of the reaction, a partial oxido radical (0.44 spins) is formed ligated to Mn. This radical is involved in a nucleophylic attack by bulk water in the OO bond reaction formation step, in which the oxido fractional unpaired electron is delocalized toward the outermost Mn of the μ-oxo bridge, instead of the ligated Mn center. The reaction then follows with a series of proton-coupled electron transfer steps, in which the oxidation state, as well as the bond strength of the OO moiety increase, while the OOMn(1) bond gets weaker until O2 is released. In this model, basic acetate ions from the buffer solution capture protons in the proton-transfer steps. In each step there is reduction of the OOMn(1) binding strength, with concomitant increase of the OO bond strength, which culminates with the release of O2 in the last step. This last step is entropy driven, while formation of hydroperoxide and superoxide moieties is enthalpy driven. According with experiments, the rate-limiting step is the double oxidation of Mn(IV,III) or peroxymonosulfate binding, which occur prior to the OO bond formation step. This supports our findings that the barriers of all intermediate steps are below the experimental barrier of 19-21kcal/mol. The implications of these findings for understanding photosynthetic water-splitting catalysis are also discussed. Copyright © 2017 Elsevier Inc. All rights reserved.

  16. [Study on optimization of the hydrolysis process of dioscin catalyzed by hydrochloric acid]. (United States)

    Li, Qian; Gao, Xiang-Tao; Zhao, Wen-Lei; Liu, Xiu-Hua


    To study the optimization of hydrolysis process of dioscin catalyzed by hydrochloric acid. The effects of hydrochloric acid concentration, reaction temperature, reaction time and their interactions had been investigated using orthogonal design and single-factor experiments. The optimum hydrolysis conditions were as follows: reaction temperature 90 degrees C, reaction time 3h, hydrochloric acid concentration 2.0 mol/L. Hydrochloric acid concentration and reaction temperature should be controlled because of their remarkable influence on hydrolysis process.

  17. PEG1000-Based Dicationic Acidic Ionic Liquid Catalyzed One-Pot Synthesis of 4-Aryl-3-Methyl-1-Phenyl-1H-Benzo[h]pyrazolo [3,4-b]quinoline-5,10-Diones via Multicomponent Reactions

    Directory of Open Access Journals (Sweden)

    Yi-Ming Ren


    Full Text Available A novel and green approach for efficient and rapid synthesis of 4-aryl-3-methyl-1-phenyl-1H-benzo[h]pyrazolo[3,4-b]quinoline-5,10-diones has been accomplished by the one-pot condensation reaction of aromatic aldehydes, 3-methyl-1-phenyl-1H-pyrazol-5-amine and 2-hydroxynaphthalene-1,4-dione using PEG1000-based dicationic acidic ionic liquid (PEG1000-DAIL as a catalyst was reported. Recycling studies have shown that the PEG1000-DAIL can be readily recovered and reused several times without significant loss of activity. The key advantages are the short reaction time, high yields, simple workup, and recovered catalyst.

  18. Fe(II/Et3N-Relay-catalyzed domino reaction of isoxazoles with imidazolium salts in the synthesis of methyl 4-imidazolylpyrrole-2-carboxylates, its ylide and betaine derivatives

    Directory of Open Access Journals (Sweden)

    Ekaterina E. Galenko


    Full Text Available A simple approach was developed for the synthesis of methyl 4-imidazolylpyrrole-2-carboxylates from easily available compounds, 5-methoxyisoxazoles and phenacylimidazolium salts under hybrid Fe(II/Et3N relay catalysis. The products were easily transformed into the corresponding 3-(5-methoxycarbonyl-1H-imidazol-3-ium-3-ylpyrrol-1-ides, which in turn can be hydrolyzed under basic conditions into the corresponding betaines. A carbene tautomeric form of the 4-methoxycarbonyl-substituted imidazolylpyrrolides was trapped by reaction with sulfur affording the corresponding imidazolethiones under very mild conditions.

  19. Mechanistic Comparison Between Pd-Catalyzed Ligand Directed C-H Chlorination and C-H Acetoxylation (United States)

    Stowers, Kara J.; Sanford, Melanie S.


    This communication describes detailed investigations of the mechanism of the Pd-catalyzed C-H chlorination and acetoxylation of 2-ortho-tolylpyridine. Under the conditions examined, both reactions proceed via rate limiting cyclopalladation. However, substrate and catalyst order as well as Hammett data indicate that the intimate mechanism of cyclopalladation differs significantly between PdCl2-catalyzed chlorination and Pd(OAc)2-catalyzed acetoxylation. PMID:19754074

  20. A facile synthesis of new 5-aryl-thiophenes bearing sulfonamide moiety via Pd(0-catalyzed Suzuki–Miyaura cross coupling reactions and 5-bromothiophene-2-acetamide: As potent urease inhibitor, antibacterial agent and hemolytically active compounds

    Directory of Open Access Journals (Sweden)

    Mnaza Noreen


    Full Text Available The present study reports a convenient approach for the synthesis of thiophene sulfonamide derivatives (3a–3k via Suzuki cross coupling reaction. This method of synthesis involved the reactions of various aryl boronic acids and esters with 5-bromthiophene-2-sulfonamide (2 under mild and suitable temperature conditions. The compounds synthesized in the present study were subjected to urease inhibition and hemolytic activities. The substitution pattern and the electronic effects of different functional groups (i.e., Cl, CH3, OCH3, F etc. available on the aromatic ring are found to have significant effect on the overall results. The compound 5-Phenylthiophene-2-sulfonamide 3a showed the highest urease inhibition activity with IC50 value ∼ 30.8 μg/mL compared with the thiourea (used as standard having IC50 value ∼ 43 μg/mL. Moreover, almost all of the compounds were examined for the hemolytic activity against triton X-100 with positive results obtained in most of the cases. In addition, the antibacterial activities of the derivatives of 5-arylthiophene-2-sulfonamide and 5-bromothiophene-2-acetamide were also investigated during the course of the study.

  1. Lipase-catalyzed production of lysophospholipids

    Directory of Open Access Journals (Sweden)

    Mnasri Taha


    Full Text Available Lysophospholipids, such as lysophosphatidic acid or lysophosphatidylcholine, are important bioactive lipids, involved in various normal and pathological cellular processes. They also have industrial and pharmaceutical uses such as emulsifiers or components of drug delivery systems. Lipases, which natural substrates are long chain triacylglycerols, are important biocatalysts for organic synthesis mainly due to their broad substrate specificity and their ability to display high catalytic activity in organic media. This paper describes the various lipase-catalyzed reactions implemented for the production of lysophospholipids. They include hydrolysis or alcoholysis of phospholipids and acylation of the glycerophosphoryl moiety. Special emphasis is made on our work dealing with the production of lysophospholipids rich in dososahexaenoic acid, an important dietary polyunsaturated fatty acid via the hydrolysis of phospholipids extracted from the microalga Isochrysis galbana.

  2. Mecanismo de fotodegradação de compostos orgânicos catalisada por TiO2 Mechanism reactions of photodegradation of organic compounds catalyzed by TiO2

    Directory of Open Access Journals (Sweden)

    Roberta Lourenço Ziolli


    Full Text Available Conventional technology used in the treatment of wastewater has been pointed as a major environmental problem for sustainable development, since minimization is not addressed accordingly. Advanced oxidation processes (AOP, based on the formation of hydroxyl radical (•OH, a powerful oxidant agent, have been considered to be a potential technology for the destruction of many toxic compounds. Photocatalysis using solar light, an AOP, has been studied for nearly 20 years and recently attracted great interest as a clean-up technology. However, solar detoxification processes have not yet achieved commercial success. This article presents an overview of reaction mechanisms at the surface of semiconductors used as photocatalysts (specially TiO2, when heterogeneous photocatalysis is used to remove hazardous compounds from contaminated sites.

  3. Mechanism of Intramolecular Rhodium- and Palladium-Catalyzed Alkene Alkoxyfunctionalizations

    KAUST Repository

    Vummaleti, Sai V. C.


    Density functional theory calculations have been used to investigate the reaction mechanism for the [Rh]-catalyzed intramolecular alkoxyacylation ([Rh] = [RhI(dppp)+] (dppp, 1,3-bis(diphenylphosphino)propane) and [Pd]/BPh3 dual catalytic system assisted intramolecular alkoxycyanation ([Pd] = Pd-Xantphos) using acylated and cyanated 2-allylphenol derivatives as substrates, respectively. Our results substantially confirm the proposed mechanism for both [Rh]- and [Pd]/ BPh3-mediated alkoxyfunctionalizations, offering a detailed geometrical and energetical understanding of all the elementary steps. Furthermore, for the [Rh]-mediated alkoxyacylation, our observations support the hypothesis that the quinoline group of the substrate is crucial to stabilize the acyl metal complex and prevent further decarbonylation. For [Pd]/BPh3-catalyzed alkoxycyanation, our findings clarify how the Lewis acid BPh3 cocatalyst accelerates the only slow step of the reaction, corresponding to the oxidative addition of the cyanate O-CN bond to the Pd center. © 2015 American Chemical Society.

  4. Lipase-Catalyzed Kinetic Resolution of Aryltrimethylsilyl Chiral Alcohols

    Directory of Open Access Journals (Sweden)

    Leandro H. Andrade


    Full Text Available Lipase-catalyzed kinetic resolution of aryltrimethylsilyl chiral alcohols through a transesterification reaction was studied. The optimal conditions found for the kinetic resolution of m- and p-aryltrimethylsilyl chiral alcohols, led to excellent results, high conversions (c = 50%, high enantiomeric ratios (E > 200 and enantiomeric excesses for the remaining (S-alcohol and (R-acetylated product (>99%. However, kinetic resolution of o-aryltrimethylsilyl chiral alcohols did not occur under the same conditions applied to the other isomers.

  5. Gold-catalyzed cyclization of allenyl acetal derivatives

    Directory of Open Access Journals (Sweden)

    Dhananjayan Vasu


    Full Text Available The gold-catalyzed transformation of allenyl acetals into 5-alkylidenecyclopent-2-en-1-ones is described. The outcome of our deuterium labeling experiments supports a 1,4-hydride shift of the resulting allyl cationic intermediates because a complete deuterium transfer is observed. We tested the reaction on various acetal substrates bearing a propargyl acetate, giving 4-methoxy-5-alkylidenecyclopent-2-en-1-ones 4 via a degradation of the acetate group at the allyl cation intermediate.

  6. Study of selective oxidation of methane catalyzed by solid superacid in unique reaction field; Tokushu hannoba no kotai chokyosan wo mochiiru methane no sentaku sanka hanno ni kansuru kenkyu

    Energy Technology Data Exchange (ETDEWEB)

    Misonoo, M.; Tatsumi, T.; Mizuno, T.; Inumaru, T. [The University of Tokyo, Tokyo (Japan)


    Selective oxidation of lower alkanes by use of heteropolymeric compounds is studied. Alkanes are activated on Cs2.5H0.5PW12O40 serving as catalyst, and their activity and selectivity improve when the catalyst is developed into a dual function catalyst in which Cs and Pt are combined. A success is reported of the synthesis of a heteropolymeric acid in which two molecules of the coordination element wolfram are replaced with a transition metal of the first period, on which acid the oxidation of cyclohexane is enhanced. Cs2.5Ni0.08H1.34PVMo11O40 as a metal/heteropolymeric acid dual function catalyst enables the direct oxidation (9% recovered at 340{degree}C) of isobutane into a methacrylic acid, which is attributed to the harmonious coordination of the oxidizing work of the catalyst and acidity. It is possible to oxidize propane into the acrylic acid, but not ethane into the acetic acid. In the case of Pd/Cs2.5H1.5PVMo11O40, the formic acid, methanol, etc., are produced upon addition of hydrogen to the system. This reaction in the hydrogen/oxygen system is supposed to take place via activated oxygen seeds as in the case of oxidation by hydrogen peroxide. 10 refs.

  7. Recent developments in copper-catalyzed radical alkylations of electron-rich π-systems

    Directory of Open Access Journals (Sweden)

    Kirk W. Shimkin


    Full Text Available Recently, a number of papers have emerged demonstrating copper-catalyzed alkylation reactions of electron-rich small molecules. The processes are generally thought to be related to long established atom-transfer radical reactions. However, unlike classical reactions, these new transformations lead to simple alkylation products. This short review will highlight recent advances in alkylations of nitronate anions, alkenes and alkynes, as well as discuss current mechanistic understanding of these novel reactions.

  8. Base catalyzed synthesis of bicyclo[3.2.1]octane scaffolds. (United States)

    Boehringer, Régis; Geoffroy, Philippe; Miesch, Michel


    The base-catalyzed reaction of achiral 1,3-cyclopentanediones tethered to activated olefins afforded in high yields bicyclo[3.2.1]octane-6,8-dione or bicyclo[3.2.1]octane-6-carboxylate derivatives bearing respectively three or five stereogenic centers. The course of the reaction is closely related to the reaction time and to the base involved in the reaction.

  9. Palladium(0)-catalyzed single and double isonitrile insertion: a facile synthesis of benzofurans, indoles, and isatins. (United States)

    Senadi, Gopal Chandru; Hu, Wan-Ping; Boominathan, Siva Senthil Kumar; Wang, Jeh-Jeng


    A palladium(0)-catalyzed cascade process consisting of isonitrile insertion and α-Csp(3)-H cross-coupling can be achieved for the synthesis of benzofurans and indoles. The construction of isatins by a Pd-catalyzed cascade reaction incorporating double isonitrile insertion, amination, and hydrolysis has also been achieved. The key features of this work include diverse heterocycle synthesis, phosphine-ligand-free reaction conditions, a one-pot procedure, simple and commercially available starting materials, broad functional-group compatibility, and moderate to good reaction yields. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Manganese-Catalyzed Aerobic Heterocoupling of Aryl Grignard Reagents

    DEFF Research Database (Denmark)

    Ghaleshahi, Hajar Golshahi; Antonacci, Giuseppe; Madsen, Robert


    An improved protocol has been developed for the MnCl2-catalyzed cross-coupling reaction of two arylmagnesium bromides under dioxygen. The reaction was achieved by using the Grignard reagents in a 2:1 ratio and 20 % of MnCl2. Very good yields of the heterocoupling product were obtained when...... the limiting Grignard reagent underwent little homocoupling under the reaction conditions. Arylmagnesium bromides that contain p-methoxy, p-(dimethylamino), p-fluoro, and p-chloro substituents were shown to afford high product yields in the cross-coupling reactions with a variety of substituted aryl Grignard...... reagents. Heterocyclic Grignard reagents, on the other hand, were less effective substrates for this transformation because of the rapid homocoupling of these reagents under the reaction conditions....

  11. Efficient TCT-catalyzed Synthesis of 1,5-Benzodiazepine Derivatives under Mild Conditions

    Directory of Open Access Journals (Sweden)

    Ching-Fa Yao


    Full Text Available 2,4,6-Trichloro-1,3,5-triazine (TCT efficiently catalyzed the condensation reactions between 1,2-diamines and various enolizable ketones to afford 1,5-benzodiazepines in good to excellent yields. Simple and mild reaction conditions, the use of a cheap catalyst and easy workup and isolation are notable features of this method.

  12. Palladium-Catalyzed Polyfluorophenylation of Porphyrins with Bis(polyfluorophenylzinc Reagents

    Directory of Open Access Journals (Sweden)

    Toshikatsu Takanami


    Full Text Available A facile and efficient method for the synthesis of pentafluorophenyl- and related polyfluorophenyl-substituted porphyrins has been achieved via palladium-catalyzed cross-coupling reactions of brominated porphyrins with bis(polyfluorophenylzinc reagents. The reaction is applicable to a variety of free-base bromoporphyrins, their metal complexes, and a number of bis(polyfluorophenylzinc reagents.

  13. A DFT study on the mechanism of palladium-catalyzed divergent ...

    Indian Academy of Sciences (India)

    gent reactions reported by Liang group. Here, we present a detailed DFT study on the mechanism of palladium-catalyzed reaction of enyne carbonates to give the corresponding vinylidenepyridines or vinyli- denepyrrolidines based on the experiment reported by. Liang et al. In the experimental studies, Pd(dba)2 was. 547 ...

  14. Degradation of acid red 14 by silver ion-catalyzed peroxydisulfate oxidation in an aqueous solution


    RASOULIFARD, Mohammad Hossein; MOHAMMADI, Seied Mohammad Mahdi DOUST


    Silver ion (Ag1+)-catalyzed peroxydisulfate was studied for the degradation of acid red 14 (AR-14) in an aqueous medium. The effect of different parameters, such as temperature, peroxydisulfate concentration, and dye and Ag1+ concentrations, were investigated. Application of Ag1+-catalyzed peroxydisulfate, as an advanced oxidation process, introduces an effectual method for wastewater treatment. An accelerated reaction using S2O82- to destroy dyes can be achieved via chemical activat...

  15. One-pot gold-catalyzed synthesis of 3-silylethynyl indoles from unprotected o-alkynylanilines

    Directory of Open Access Journals (Sweden)

    Jérôme Waser


    Full Text Available The Au(III-catalyzed cyclization of 2-alkynylanilines was combined in a one-pot procedure with the Au(I-catalyzed C3-selective direct alkynylation of indoles using the benziodoxolone reagent TIPS-EBX to give a mild, easy and straightforward entry to 2-substituted-3-alkynylindoles. The reaction can be applied to unprotected anilines, was tolerant to functional groups and easy to carry out (RT, and requires neither an inert atmosphere nor special solvents.

  16. Red Seaweed Enzyme-Catalyzed Bromination of Bromophenol Red: An Inquiry-Based Kinetics Laboratory Experiment for Undergraduates (United States)

    Jittam, Piyachat; Boonsiri, Patcharee; Promptmas, Chamras; Sriwattanarothai, Namkang; Archavarungson, Nattinee; Ruenwongsa, Pintip; Panijpan, Bhinyo


    Haloperoxidase enzymes are of interest for basic and applied bioscientists because of their increasing importance in pharmaceutical industry and environmental cleanups. In a guided inquiry-based laboratory experiment for life-science, agricultural science, and health science undergraduates, the bromoperoxidase from a red seaweed was used to…

  17. Ketone-catalyzed photochemical C(sp3)-H chlorination. (United States)

    Han, Lei; Xia, Jibao; You, Lin; Chen, Chuo


    Photoexcited arylketones catalyze the direct chlorination of C(sp3)-H groups by N-chlorosuccinimide. Acetophenone is the most effective catalyst for functionalization of unactivated C-H groups while benzophenone provides better yields for benzylic C-H functionalization. Activation of both acetophenone and benzophenone can be achieved by irradiation with a household compact fluorescent lamp. This light-dependent reaction provides a better control of the reaction as compared to the traditional chlorination methods that proceed through a free radical chain propagation mechanism.

  18. Asymmetric Propargylation of Ketones using Allenylboronates Catalyzed by Chiral Biphenols (United States)

    Barnett, David S.; Schaus, Scott E.


    Chiral biphenols catalyze the enantioselective asymmetric propargylation of ketones using allenylboronates. The reaction uses 10 mol % of 3,3′-Br2-BINOL as the catalyst and allenyldioxoborolane as the nucleophile, in the absence of solvent, and under microwave irradiation to afford the homopropargylic alcohol. The reaction products are obtained in good yields (60 – 98%) and high enantiomeric ratios (3:1 – 99:1). Diastereoselective propargylations using chiral racemic allenylboronates result in good diastereoselectivities (dr > 86:14) and enantioselectivities (er > 92:8) under the catalytic conditions. PMID:21732609

  19. Zeolite-catalyzed isomerization of tetroses in aqueous medium

    DEFF Research Database (Denmark)

    Shunmugavel, Saravanamurugan; Riisager, Anders


    in water. Hence, the results demonstrate water to be a preferred solvent compared to lower alcohols for zeolite-catalyzed tetrose isomerization, which is opposite to what previously have been found for analogous pentose and hexose isomerization. A reuse study revealed further that H-USY(6) could be applied...... in at least five reaction runs with essentially unchanged activity and without significant aluminium leaching from the catalyst. The use of benign reaction conditions and an industrially pertinent solid catalyst in combination with water establishes a new, green tetrose isomerization protocol...

  20. Hydroperoxide-dependent sulfoxidation catalyzed by soybean microsomes. (United States)

    Blee, E; Durst, F


    The sulfoxidation of methiocarb, an aromatic-alkyl sulfide pesticide, catalyzed by soybean microsomes was found to be strongly stimulated in the presence of cumene and linoleic acid hydroperoxides. We have shown that this S-oxidation, which does not require cofactors such as NAD(P)H, is an hydroperoxide-dependent reaction: 18O2-labeling experiments demonstrated that the oxygen atom incorporated into the sulfoxide originated from hydroperoxides rather than from molecular oxygen. In the absence of exogenous hydroperoxides, soybean microsomes catalyzed methiocarb sulfoxide formation at a basal rate dependent on their endogenous hydroperoxides, especially those derived from free fatty acids. The nature of the sulfoxidase is discussed. Our results seem to rule out the participation of cytochrome P-450 in this oxidation, whereas the studied sulfoxidase presents some similarities to plant peroxygenase.

  1. Post-Ugi gold-catalyzed diastereoselective domino cyclization for the synthesis of diversely substituted spiroindolines

    Directory of Open Access Journals (Sweden)

    Amit Kumar


    Full Text Available An Ugi four-component reaction of propargylamine with 3-formylindole and various acids and isonitriles produces adducts which are subjected to a cationic gold-catalyzed diastereoselective domino cyclization to furnish diversely substituted spiroindolines. All the reactions run via an exo-dig attack in the hydroarylation step followed by an intramolecular diastereoselective trapping of the imminium ion. The whole sequence is atom economic and the application of a multicomponent reaction assures diversity.

  2. Renalase does not catalyze the oxidation of catecholamines. (United States)

    Beaupre, Brett A; Hoag, Matthew R; Moran, Graham R


    It is widely accepted that the function of human renalase is to oxidize catecholamines in blood. However, this belief is based on experiments that did not account for slow, facile catecholamine autoxidation reactions. Recent evidence has shown that renalase has substrates with which it reacts rapidly. The reaction catalyzed defines renalase as an oxidase, one that harvests two electrons from either 2-dihydroNAD(P) or 6-dihydroNAD(P) to form β-NAD(P)(+) and hydrogen peroxide. The apparent metabolic purpose of such a reaction is to avoid inhibition of primary dehydrogenase enzymes by these β-NAD(P)H isomers. This article demonstrates that renalase does not catalyze the oxidation of neurotransmitter catecholamines. Using high-performance liquid chromatography we show that there is no evidence of consumption of epinephrine by renalase. Using time-dependent spectrophotometry we show that the renalase FAD cofactor spectrum is unresponsive to added catecholamines, that adrenochromes are not observed to accumulate in the presence of renalase and that the kinetics of single turnover reactions with 6-dihydroNAD are unaltered by the addition of catecholamines. Lastly we show using an oxygen electrode assay that plasma renalase activity is below the level of detection and only when exogenous renalase and 6-dihydroNAD are added can dioxygen be observed to be consumed. Copyright © 2015 Elsevier Inc. All rights reserved.

  3. Deoxyribonucleoside kinases: two enzyme families catalyze the same reaction

    DEFF Research Database (Denmark)

    Sandrini, Michael; Piskur, Jure


    Mammals have four deoxyribonucleoside kinases, the cytoplasmic (TK1) and mitochondrial (TK2) thymidine kinases, and the deoxycytidine (dCK) and deoxyguanosine (dGK) kinases, which salvage the precursors for nucleic acids synthesis. In addition to the native deoxyribonucleoside substrates, the kin...

  4. Tributylphosphine-catalyzed reaction of ethanethiol with alkynyl ketones

    Institute of Scientific and Technical Information of China (English)

    Shen Zhao; Qing Fa Zhou; Jia Zhi Liu; Wei Fang Tang; Tao Lu


    A stereoselective and effective method for the synthesis of vinyl thioethers has been developed. This method is based on the Michael addition of ethanethiol to various alkynyl ketones using 10 mol% of tributylphosphine as catalyst. Most of alkynyl ketones react with ethanethiol in this system to yield mainly Z-isomer of vinyl thioether adducts, only in one case mainly E-isomer of vinyl thioether adducts was observed.

  5. Resting state and elementary steps of the coupling of aryl halides with thiols catalyzed by alkylbisphosphine complexes of palladium. (United States)

    Alvaro, Elsa; Hartwig, John F


    Detailed mechanistic studies on the coupling of aryl halides with thiols catalyzed by palladium complexes of the alkylbisphosphine ligand CyPF-(t)Bu (1-dicyclohexylphosphino-2-di-tert-butylphosphinoethylferrocene) are reported. The elementary steps that constitute the catalytic cycle, i.e. oxidative addition, transmetalation and reductive elimination, have been studied, and their relative rates are reported. Each of the steps of the catalytic process occurs at temperatures that are much lower than those required for the reactions catalyzed by a combination of palladium precursors and CyPF-(t)Bu. To explain these differences in rates between the catalytic and stoichiometric reactions, studies were conducted to identify the resting state of the catalyst of the reactions catalyzed by a combination of Pd(OAc)(2) and CyPF-(t)Bu, a combination of Pd(dba)(2) and CyPF-(t)Bu, or the likely intermediate Pd(CyPF-(t)Bu)(Ar)(Br). These data show that the major palladium complex in each case lies off of the catalytic cycle. The resting state of the reactions catalyzed by Pd(OAc)(2) and CyPF-(t)Bu was the palladium bis-thiolate complex [Pd(CyPF-(t)Bu)(SR)(2)] (R = alkyl or aryl). The resting state in reactions catalyzed by Pd(2)(dba)(3) and CyPF-(t)Bu was the binuclear complex [Pd(CyPF-(t)Bu)](2)(mu(2),eta(2)-dba) (9). The resting states of reactions of both aromatic and aliphatic thiols catalyzed by [Pd(CyPF-(t)Bu)(p-tolyl)(Br)] (3a) were the hydridopalladium thiolate complexes [Pd(CyPF-(t)Bu)(H)(SR)] (R= alkyl and aryl). All these palladium species have been prepared independently, and the mechanisms by which they enter the catalytic cycle have been examined in detail. These features of the reaction catalyzed by palladium and CyPF-(t)Bu have been compared with those of reactions catalyzed by the alkylbisphosphine DiPPF and Pd(OAc)(2) or Pd(dba)(2). Our data indicate that the resting states of these reactions are similar to each other and that our mechanistic conclusions about

  6. Synthesis of Fluoroalkoxy Substituted Arylboronic Esters by Iridium-Catalyzed Aromatic C–H Borylation

    KAUST Repository

    Batool, Farhat


    The preparation of fluoroalkoxy arylboronic esters by iridium-catalyzed aromatic C–H borylation is described. The fluoroalkoxy groups employed include trifluoromethoxy, difluoromethoxy, 1,1,2,2-tetrafluoroethoxy, and 2,2-difluoro-1,3-benzodioxole. The borylation reactions were carried out neat without the use of a glovebox or Schlenk line. The regioselectivities available through the iridium-catalyzed C–H borylation are complementary to those obtained by the electrophilic aromatic substitution reactions of fluoroalkoxy arenes. Fluoroalkoxy arylboronic esters can serve as versatile building blocks.

  7. Silver-Catalyzed Dehydrogenative Synthesis of Carboxylic Acids from Primary Alcohols

    DEFF Research Database (Denmark)

    Ghalehshahi, Hajar Golshadi; Madsen, Robert


    A simple silver-catalyzed protocol has been developed for the acceptorless dehydrogenation of primary alcohols into carboxylic acids and hydrogen gas. The procedure uses 2.5 % Ag2 CO3 and 2.5-3 equiv of KOH in refluxing mesitylene to afford the potassium carboxylate which is then converted...... into the acid with HCl. The reaction can be applied to a variety of benzylic and aliphatic primary alcohols with alkyl and ether substituents, and in some cases halide, olefin, and ester functionalities are also compatible with the reaction conditions. The dehydrogenation is believed to be catalyzed by silver...

  8. Heterogeneous base-catalyzed methanolysis of vegetable oils: State of art

    Directory of Open Access Journals (Sweden)

    Miladinović Marija R.


    Full Text Available Today, homogeneous base-catalyzed methanolysis is most frequently used method for industrial biodiesel production. High requirements for the quality of feedstocks and the problems related to a huge amount of wastewaters have led to the development of novel biodiesel production technologies. Among them, the most important is heterogeneous base-catalyzed methanolysis, which has been intensively investigated in the last decade in order to develop new catalytic systems, to optimize the reaction conditions and to recycle catalysts. These studies are a base for developing continuous biodiesel production on industrial scale in near future. The present work summarizes up-to-date studies on biodiesel production by heterogeneous base-catalyzed methanolysis. The main goals were to point out the application of different base compounds as catalysts, the methods of catalyst preparation, impregnation on carriers and recycling as well as the possibilities to improve existing base-catalyzed biodiesel production processes and to develop novel ones.

  9. Probing the critical residues for intramolecular fructosyl transfer reaction of a levan fructotransferase

    National Research Council Canada - National Science Library

    Moon, Keum-Ok; Choi, Kyoung-Hwa; Kang, Ho-Young; Oh, Jeong-Il; Jang, Se Bok; Park, Cheon-Seok; Lee, Jong-Hoon; Cha, Jaeho


    Levan fructotransferase (LFTase) preferentially catalyzes the transfructosylation reaction in addition to levan hydrolysis, whereas other levan-degrading enzymes hydrolyze levan into a levan-oligosaccharide and fructose...

  10. Molecular basis for chloronium-mediated meroterpene cyclization: cloning, sequencing, and heterologous expression of the napyradiomycin biosynthetic gene cluster. (United States)

    Winter, Jaclyn M; Moffitt, Michelle C; Zazopoulos, Emmanuel; McAlpine, James B; Dorrestein, Pieter C; Moore, Bradley S


    Structural inspection of the bacterial meroterpenoid antibiotics belonging to the napyradiomycin family of chlorinated dihydroquinones suggests that the biosynthetic cyclization of their terpenoid subunits is initiated via a chloronium ion. The vanadium-dependent haloperoxidases that catalyze such reactions are distributed in fungi and marine algae and have yet to be characterized from bacteria. The cloning and sequence analysis of the 43-kb napyradiomycin biosynthetic cluster (nap) from Streptomyces aculeolatus NRRL 18422 and from the undescribed marine sediment-derived Streptomyces sp. CNQ-525 revealed 33 open reading frames, three of which putatively encode vanadium-dependent chloroperoxidases. Heterologous expression of the CNQ-525-based nap biosynthetic cluster in Streptomyces albus produced at least seven napyradiomycins, including the new analog 2-deschloro-2-hydroxy-A80915C. These data not only revealed the molecular basis behind the biosynthesis of these novel meroterpenoid natural products but also resulted in the first in vivo verification of vanadium-dependent haloperoxidases.


    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

  12. Mechanisms of bacterially catalyzed reductive dehalogenation

    Energy Technology Data Exchange (ETDEWEB)

    Picardal, Flynn William [Univ. of Arizona, Tucson, AZ (United States)


    Nine bacteria were tested for the ability to dehalogenate tetrachloromethane (CT), tetrachloroethene (PCE), and 1, 1, 1-trichloroethane (TCA) under anaerobic conditions. Three bacteria were able to reductively dehalogenate CT. Dehalogenation ability was not readily linked to a common metabolism or changes in culture redox potential. None of the bacteria tested were able to dehalogenate PCE or TCA. One of the bacteria capable of dehalogenating CT, Shewanella putrefaciens, was chosen as a model organism to study mechanisms of bacterially catalyzed reductive dehalogenation. The effect of a variety of alternate electron acceptors on CT dehalogenation ability by S. putrefaciens was determined. oxygen and nitrogen oxides were inhibitory but Fe (III), trimethylamine oxide, and fumarate were not. A model of the electron transport chain of S. putrefaciens was developed to explain inhibition patterns. A period of microaerobic growth prior to CT exposure increased the ability of S. putrefaciens to dehalogenate CT. A microaerobic growth period also increased cytochrome concentrations. A relationship between cytochrome content and dehalogenation ability was developed from studies in which cytochrome concentrations in S. putrefaciens were manipulated by changing growth conditions. Stoichiometry studies using 14C-CT suggested that CT was first reduced to form a trichloromethyl radical. Reduction of the radical to produce chloroform and reaction of the radical with cellular biochemicals explained observed product distributions. Carbon dioxide or other fully dehalogenated products were not found.

  13. Palladium-catalyzed asymmetric Heck arylation of 2,3-dihydrofuran--effect of prolinate salts. (United States)

    Morel, Adam; Silarska, Ewelina; Trzeciak, Anna M; Pernak, Juliusz


    Chiral ionic liquids (CILs) containing L-prolinate and L-lactate anions and non-chiral quaternary ammonium cations were employed in the palladium catalyzed enantioselective Heck arylation of 2,3-dihydrofuran with aryl iodides (iodobenzene, 4-iodotoluene, 2-iodoanisole, 4-iodoanisole, 4-iodoacetophenone). In all the reactions 2-aryl-2,3-dihydrofuran (3) was obtained as the main product with the yield up to 52% at the total conversion reaching 83%. Product 3, 2-phenyl-2,3-dihydrofuran, was obtained with excellent enantioselectivity (>99% ee) in a 6 h reaction with tetrabutylammonium L-prolinate. In the proposed homogeneous reaction Pd(0) nanoparticles are considered as a resting state of the catalyst and a source of soluble palladium species catalyzing the Heck reaction. The yield and stereoselectivity of the Heck reaction are strongly influenced by the kind of non-chiral cations present in CILs.

  14. Mechanistic insight into benzenethiol catalyzed amide bond formations from thioesters and primary amines

    DEFF Research Database (Denmark)

    Stuhr-Hansen, Nicolai; Bork, Nicolai; Strømgaard, Kristian


    The influence of arylthiols on cysteine-free ligation, i.e. the reaction between an alkyl thioester and a primary amine forming an amide bond, was studied in a polar aprotic solvent. We reacted the ethylthioester of hippuric acid with cyclohexylamine in the absence or presence of various quantities...... of thiophenol (PhSH) in a slurry of disodium hydrogen phosphate in dry DMF. Quantitative conversions into the resulting amide were observed within a few hours in the presence of equimolar amounts of thiophenol. Ab initio calculations showed that the reaction mechanism in DMF is similar to the well-known aqueous...... reaction mechanism. The energy barrier of the catalyzed amidation reaction is approximately 40 kJ mol(-1) lower than the non-catalyzed amidation reaction. At least partially this can be explained by a hydrogen bond from the amine to the π-electrons of the thiophenol, stabilizing the transition state...

  15. Palladium-catalyzed anti-Markovnikov oxidation of terminal alkenes. (United States)

    Dong, Jia Jia; Browne, Wesley R; Feringa, Ben L


    The palladium-catalyzed oxidation of alkenes, the Wacker-Tsuji reaction, is undoubtedly a classic in organic synthesis and provides reliable access to methyl ketones from terminal alkenes under mild reaction conditions. Methods that switch the selectivity of the reaction to provide the aldehyde product are desirable because of the access they provide to a valuable functional group, however such methods are elusive. Herein we survey both the methods which have been developed recently in achieving such selectivity and discuss common features and mechanistic insight which offers promise in achieving the goal of a general method for anti-Markovnikov-selective olefin oxidations. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Manganese-Catalyzed Upgrading of Ethanol into 1-Butanol. (United States)

    Fu, Shaomin; Shao, Zhihui; Wang, Yujie; Liu, Qiang


    Biomass-derived ethanol is an important renewable feedstock. Its conversion into high-quality biofuels is a promising route to replace fossil resources. Herein, an efficient manganese-catalyzed Guerbet-type condensation reaction of ethanol to form 1-butanol was explored. This is the first example of upgrading ethanol into higher alcohols using a homogeneous non-noble-metal catalyst. This process proceeded selectively in the presence of a well-defined manganese pincer complex at the parts per million (ppm) level. The developed reaction represents a sustainable synthesis of 1-butanol with excellent turnover number (>110 000) and turnover frequency (>3000 h(-1)). Moreover, mechanistic studies including control experiments, NMR spectroscopy, and X-ray crystallography identified the essential role of the "N-H moiety" of the manganese catalysts and the major reaction intermediates related to the catalytic cycle.

  17. Quinone-Catalyzed Selective Oxidation of Organic Molecules. (United States)

    Wendlandt, Alison E; Stahl, Shannon S


    Quinones are common stoichiometric reagents in organic chemistry. Para-quinones with high reduction potentials, such as DDQ and chloranil, are widely used and typically promote hydride abstraction. In recent years, many catalytic applications of these methods have been achieved by using transition metals, electrochemistry, or O2 to regenerate the oxidized quinone in situ. Complementary studies have led to the development of a different class of quinones that resemble the ortho-quinone cofactors in copper amine oxidases and mediate the efficient and selective aerobic and/or electrochemical dehydrogenation of amines. The latter reactions typically proceed by electrophilic transamination and/or addition-elimination reaction mechanisms, rather than hydride abstraction pathways. The collective observations show that the quinone structure has a significant influence on the reaction mechanism and has important implications for the development of new quinone reagents and quinone-catalyzed transformations. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Controlled enzyme catalyzed heteropolysaccharide degradation

    DEFF Research Database (Denmark)

    Rasmussen, Louise Enggaard

    of the progress of enzymatic hydrolysis of different xylan substrates was developed. The method relies on dividing the HPSEC elution profiles into fixed time intervals and utilizing the linear refractive index response (area under the curve) of defined standard compounds. In order to obtain optimal high......-performance size exclusion chromatography profiles, the method was designed using 0.1 M CH3COONa in both the mobile phase and as the sample solution. This was based on the systematic evaluation of the influence of the mobile phase, including the type, ionic strength and pH, on the refractive index detector...... response. A time study of the enzyme catalyzed hydrolysis of birchwood xylan and wheat bran by BsX was used as an example to demonstrate the workability of the new HPSEC method for obtaining progress curves describing the evolution in the product profile during enzyme catalysis. Flaxseed mucilage (FM) has...

  19. Palladium-Catalyzed Directed Halogenation of Bipyridine N-Oxides. (United States)

    Zucker, Sina P; Wossidlo, Friedrich; Weber, Manuela; Lentz, Dieter; Tzschucke, C Christoph


    The palladium-catalyzed directed C-H halogenation of bipyridine N-oxides was investigated. Using NCS or NBS (N-chloro- or N-bromosuccinimide) and 5 mol % Pd(OAc)2 in chlorobenzene (0.10 molar) at 110 °C, pyridine-directed functionalization took place and 3-chloro- or 3-bromobipyridine N-oxides were obtained in high yields. The reaction is sensitive to steric hindrance by 4- and 6'-substituents. Only in the latter case, where coordination of palladium by the pyridine is hindered, 3'-halogenation directed by the N-oxide function was observed. The halogenated products were deoxygenated by PCl3 or PBr3.

  20. Iodine - catalyzed prins cyclization of aliphatic and aromatic ketones

    Energy Technology Data Exchange (ETDEWEB)

    Kishore, K.R.; Reddy, K.; Silva Junior, Luiz F., E-mail: [Universidade de Sao Paulo (IQ/USP), SP (Brazil). Inst. de Quimica. Dept. de Quimica Fundamental


    Iodine-catalyzed Prins cyclization of homoallylic alcohols and ketones was investigated. Anhydrous conditions and inert atmosphere are not required in this metal-free protocol. The reaction of 2-(3,4-dihydronaphthalene-1-yl)propan-1-ol with six aliphatic symmetric ketones gave the desired products in 67-77% yield. Cyclization was performed with four aliphatic unsymmetric ketones, leading to corresponding pyrans in 66-76% yield. Prins cyclization was also accomplished with four aromatic ketones in 37-66% yield. Finally, Prins cyclization of the monoterpene isopulegol and acetone was successfully achieved. (author)

  1. Comparing Ru and Fe-catalyzed olefin metathesis

    KAUST Repository

    Poater, Albert


    Density functional theory calculations have been used to explore the potential of Fe-based complexes with an N-heterocyclic carbene ligand, as olefin metathesis catalysts. Apart from a less endothermic reaction energy profile, a small reduction in the predicted upper energy barriers (≈ 2 kcal mol -1) is calculated in the Fe catalyzed profile with respect to the Ru catalysed profile. Overall, this study indicates that Fe-based catalysts have the potential to be very effective olefin metathesis catalysts. This journal is © the Partner Organisations 2014.

  2. Ruthenium-Catalyzed Dehydrogenative Decarbonylation of Primary Alcohols

    DEFF Research Database (Denmark)

    Mazziotta, Andrea; Madsen, Robert


    Dehydrogenative decarbonylation of a primary alcohol involves the release of both dihydrogen and carbon monoxide to afford the one-carbon shorter product. The transformation has now been achieved with a ruthenium-catalyzed protocol by using the complex Ru(COD)Cl2 and the hindered monodentate ligand...... P(o-tolyl)3 in refluxing p-cymene. The reaction can be applied to both benzylic and long chain linear aliphatic alcohols. The intermediate aldehyde can be observed during the transformation, which is therefore believed to proceed through two separate catalytic cycles involving first dehydrogenation...... of the alcohol and then decarbonylation of the resulting aldehyde....

  3. Synthesis of Dihydrobenzofurans via Palladium-Catalyzed Heteroannulations

    Energy Technology Data Exchange (ETDEWEB)

    Rozhkov, Roman Vladimirovich [Iowa State Univ., Ames, IA (United States)


    Palladium-catalyzed heteroannulation of 1,3-dienes with 3-iodo-2-alkenols, and 2-iodo-2-alkenols, as well as their amino analogs, affords the corresponding cyclic ethers and amines respectively. The presence of a β-hydrogen in the vinylic halide results in β-hydride elimination giving the corresponding alkyne. The presence of a bulky group in the α-position of the vinylic halide results in failure or reduced amounts of annulation products. A chloride source, pyridine base and electron-rich phosphine are essential for this reaction.

  4. Reactivity of bromoselenophenes in palladium-catalyzed direct arylations

    Directory of Open Access Journals (Sweden)

    Aymen Skhiri


    Full Text Available The reactivity of 2-bromo- and 2,5-dibromoselenophenes in Pd-catalyzed direct heteroarylation was investigated. From 2-bromoselenophene, only the most reactive heteroarenes could be employed to prepare 2-heteroarylated selenophenes; whereas, 2,5-dibromoselenophene generally gave 2,5-di(heteroarylated selenophenes in high yields using both thiazole and thiophene derivatives. Moreover, sequential catalytic C2 heteroarylation, bromination, catalytic C5 arylation reactions allowed the synthesis of unsymmetrical 2,5-di(heteroarylated selenophene derivatives in three steps from selenophene.

  5. Palladium-Catalyzed alpha-Arylation of Tetramic Acids

    DEFF Research Database (Denmark)

    Storgaard, Morten; Dorwald, F. Z.; Peschke, B.


    A mild, racemization-free, palladium-Catalyzed alpha-arylation of tetramic acids (2,4-pyrrolidinediones) has been developed. Various amino acid-derived tetramic acids were cleanly arylated by treatment with 2 mol % of Pd(OAc)(2), 4 mol % of a sterically demanding biaryl phosphine, 2.3 equiv of K2...... no effect on their reactivity: both electron-rich and electron-poor aryl chlorides and bromides or triflates led to good yields. Ortho-substituted aryl halides and heteroaryl halides, however, did not undergo the title reaction....

  6. Muon-catalyzed fusion in deuterium at 3 K

    Energy Technology Data Exchange (ETDEWEB)

    Knowles, P.E.; Beer, G.A.; Mason, G.R.; Porcelli, T.A. [Victoria Univ., BC (Canada); Bailey, J.M. [EA Technology, Capenhurst (United Kingdom); Beveridge, J.L.; Marshall, G.M.; Mulhauser, F.; Olin, A. [British Columbia Univ., Vancouver, BC (Canada). TRIUMF Facility; Fujiwara, M.C. [British Columbia Univ., Vancouver, BC (Canada); Huber, T.M. [Gustavus Adolphus Coll., St. Peter, MN (United States); Jacot-Guillarmod, R. [Fribourg Univ. (Switzerland); Kammel, P. [Lawrence Berkeley Lab., CA (United States); Kim, S.K. [Jeonbuk National Univ. (Korea, Republic of); Kunselman, A.R. [Wyoming Univ., Laramie, WY (United States); Martoff, C.J. [Temple Univ., Philadelphia, PA (United States); Petitjean, C. [Paul Scherrer Inst. (PSI), Villigen (Switzerland); Zmeskal, J. [Oesterreichische Akademie der Wissenschaften, Vienna (Austria)


    Muon-catalyzed fusion in deuterium has traditionally been studied in gaseous and liquid targets. The TRIUMF solid hydrogen layer target system has been used to study the fusion reaction rates in the solid phase at a target temperature of 3 K. Both branches of the cycle were observed; neutrons by a liquid organic scintillator, and protons by a silicon detector located inside the target system. The effective molecular formation rate from the upper hyperfine state and the spin exchange rate have been measured, and information on the branching ratio parameters has been extracted. (orig.). 21 refs.

  7. Amino acid-catalyzed conversion of citral : cis-trans isomerization and its conversion into 6-methyl-5-hepten-2-one and acetaldehyde

    NARCIS (Netherlands)

    Wolken, W.A.M.; Have, R. ten; Werf, M.J. van der


    Under alkaline conditions, amino acids or proteins catalyze the deacetylation of citral, a major aroma component, resulting in methylheptenone and acetaldehyde formation. 3-Hydroxycitronellal is an intermediate in this reaction. Amino acids also catalyze the cis-trans isomerization of the pure

  8. Lipase-catalyzed transesterification of soybean oil and phytosterol in supercritical CO2. (United States)

    Hu, Lizhi; Llibin, Sun; Li, Jun; Qi, Liangjun; Zhang, Xu; Yu, Dianyu; Walid, Elfalleh; Jiang, Lianzhou


    The transesterification of phytosterol and soybean oil was performed using Novozym 435 in supercritical carbon dioxide (SC-CO2). The transesterification reaction was conducted in soybean oil containing 5-25% phytosterol at 55-95 °C and free-water solvent. The effects of temperature, reaction time, phytosterol concentration, lipase dosage and reaction pressure on the conversion rate of transesterification were investigated. The optimal reaction conditions were the reaction temperature (85 °C), reaction time (1 h), phytosterol concentration (5%), reaction pressure (8 Mpa) and lipase dosage (1%). The highest conversion rate of 92% could be achieved under the optimum conditions. Compared with the method of lipase-catalyzed transesterification of phytosterol and soybean oil at normal pressure, the transesterification in SC-CO2 reduced significantly the reaction temperature and reaction time.

  9. Insights into hydrogen bond donor promoted fixation of carbon dioxide with epoxides catalyzed by ionic liquids. (United States)

    Liu, Mengshuai; Gao, Kunqi; Liang, Lin; Wang, Fangxiao; Shi, Lei; Sheng, Li; Sun, Jianmin


    Catalytic coupling of carbon dioxide with epoxides to obtain cyclic carbonates is an important reaction that has been receiving renewed interest. In this contribution, the cycloaddition reaction in the presence of various hydrogen bond donors (HBDs) catalyzed by hydroxyl/carboxyl task-specific ionic liquids (ILs) is studied in detail. It was found that the activity of ILs could be significantly enhanced in the presence of ethylene glycol (EG), and EG/HEBimBr were the most efficient catalysts for the CO2 cycloaddition to propylene oxide. Moreover, the binary catalysts were also efficiently versatile for the CO2 cycloaddition to less active epoxides such as styrene oxide and cyclohexene oxide. Besides, the minimum energy paths for this hydrogen bond-promoted catalytic reaction were calculated using the density functional theory (DFT) method. The DFT results suggested that the ring-closing reaction was the rate-determining step in the HEBimBr-catalyzed cycloaddition reaction but the EG addition could remarkably reduce its energy barrier as the formation of a hydrogen bond between EG and the oxygen atom of epoxides led this process along the standard SN2 mechanism. As a result, the ring-opening reaction became the rate-determining step in the EG/HEBimBr-catalyzed cycloaddition reaction. The work reported herein helped the understanding and design of catalysts for efficient fixation of CO2 to epoxides via hydrogen bond activation.

  10. xanthen-11-ones by ZnO Nanoparticles Catalyzed Three Co

    African Journals Online (AJOL)


    tetrahydrobenzo[a]xanthen-11-ones by ZnO Nanoparticles. Catalyzed Three Component Coupling Reaction of. Aldehydes, 2-Naphthol and Dimedone. Javad Safaei-Ghomi and Mohammad Ali Ghasemzadeh. Department of Chemistry, Qom Branch, Islamic Azad University, Qom, Iran. Received 11 September 2013, revised ...

  11. Palladium-Catalyzed Enantioselective Addition of Two Distinct Nucleophiles across Alkenes Capable of Quinone Methide Formation


    Jensen, Katrina H.; Pathak, Tejas P.; Zhang, Yang; Sigman, Matthew S.


    A sequential intramolecular-intermolecular enantioselective alkene difunctionalization reaction has been developed which is thought to proceed through Pd-catalyzed quinone methide formation. The synthesis of new chiral heterocyclic compounds with adjacent chiral centers is achieved in enantiomeric ratios up to 99:1 and diastereomeric ratios up to 10:1.

  12. Synthesis of 2-substituted tetraphenylenes via transition-metal-catalyzed derivatization of tetraphenylene

    Directory of Open Access Journals (Sweden)

    Shulei Pan


    Full Text Available A new strategy for the synthesis of 2-substituted tetraphenylenes through a transition-metal-catalyzed derivatization has been developed. Three types of functionalities, including OAc, X (Cl, Br, I and carbonyl, were introduced onto tetraphenylene, which allows the easy access to a variety of monosubstituted tetraphenylenes. These reactions could accelerate research on the properties and application of tetraphenylene derivatives.

  13. Mechanistic investigation of the gold-catalyzed aerobic oxidation of alcohols

    DEFF Research Database (Denmark)

    Fristrup, Peter; Johansen, Louise Bahn; Christensen, Claus Hviid


    The mechanism for the gold-catalyzed aerobic oxidation of alcohols was studied using a series of para-substituted benzyl alcohols (Hammett methodology). The competition experiments clearly show that the rate-determining step of the reaction involves the generation of a partial positive charge in ...

  14. Atomistic Model for the Polyamide Formation from beta-Lactam Catalyzed by Candida antarctica Lipase B

    NARCIS (Netherlands)

    Baum, Iris; Elsaesser, Brigitta; Schwab, Leendert W.; Loos, Katja; Fels, Gregor; Elsässer, Brigitta

    Candida antarctica lipase B (CALB) is an established biocatalyst for a variety of transesterification, amidation, and polymerization. reactions. In contrast to polyesters, poly amides are not yet generally accessible via enzymatic polymerization. In this regard, an enzyme-catalyzed ring-opening

  15. Enzyme-Catalyzed Synthesis of Saccharide Acrylate Monomers from Nonedible Biomass

    NARCIS (Netherlands)

    Kloosterman, Wouter M. J.; Brouwer, Sander; Loos, Katja

    Various cellulase preparations were found to catalyze the transglycosidation between cotton linters and 2-hydroxyethyl acrylate. The conversion and enzyme activity were found to be optimal in reaction mixtures that contained 5 vol% of the acrylate. The structures of the products were revealed by

  16. Homocoupling of benzyl halides catalyzed by POCOP-nickel pincer complexes

    KAUST Repository

    Chen, Tao


    Two types of POCOP-nickel(II) pincer complexes were prepared by mixing POCOP pincer ligands and NiX 2 in toluene at reflux. The resulting nickel complexes efficiently catalyze the homocoupling reactions of benzyl halides in the presence of zinc. The coupled products were obtained in excellent to quantitative yields. © 2012 Elsevier Ltd. All rights reserved.

  17. Gold-catalyzed heterocyclizations in alkynyl- and allenyl-β-lactams

    Directory of Open Access Journals (Sweden)

    Pedro Almendros


    Full Text Available New gold-catalyzed methods using the β-lactam scaffold have been recently developed for the synthesis of different sized heterocycles. This overview focuses on heterocyclization reactions of allenic and alkynic β-lactams which rely on the activation of the allene and alkyne component. The mechanism as well as the regio- and stereoselectivity of the cyclizations are also discussed.

  18. Metallocene-catalyzed alkene polymerization and the observation of Zr-allyls


    Landis, Clark R.; Christianson, Matthew D.


    Single-site polymerization catalysts enable exquisite control over alkene polymerization reactions to produce new materials with unique properties. Knowledge of catalyst speciation and fundamental kinetics are essential for full mechanistic understanding of zirconocene-catalyzed alkene polymerization. Currently the effect of activators on fundamental polymerization steps is not understood. Progress in understanding activator effects requires determination of fundamental kinetics for zirconoce...

  19. Enantioselective Evans-Tishchenko Reduction of b-Hydroxyketone Catalyzed by Lithium Binaphtholate

    Directory of Open Access Journals (Sweden)

    Makoto Nakajima


    Full Text Available Lithium diphenylbinaphtholate catalyzed the enantioselective Evans-Tishchenko reduction of achiral b-hydroxyketones to afford monoacyl-protected 1,3-diols with high stereoselectivities. In the reaction of racemic b-hydroxyketones, kinetic optical resolution occurred in a highly stereoselective manner.

  20. Laccase catalyzed grafting of-N-OH type mediators to lignin via radical-radical coupling

    DEFF Research Database (Denmark)

    Munk, Line; Punt, A. M.; Kabel, M. A.


    by laccases from Trametes versicolor and Pleurotus ostreatus by quantitative analysis of the reaction outcome by pyrolysis gas chromatography mass spectroscopy. The two laccases were equally efficient in catalyzing grafting, but only-N-OH type mediators grafted. HPI (N-hydroxyacetanilide) grafted 7-10 times...