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Sample records for asymmetric horner-wadsworth-emmons reactions

  1. Reagent Control of Geometric Selectivity and Enantiotopic Group Preference in Asymmetric Horner-Wadsworth-Emmons Reactions with meso-Dialdehydes

    DEFF Research Database (Denmark)

    Tullis, Joshua S.; Vares, Lauri; Kann, Nina

    1998-01-01

    Results from asymmetric Horner-Wadsworth-Emmons reactions between chiral phosphonate reagents 3a-d, which contain (1R,2S,5R)-8-phenylmenthol as a chiral auxiliary, and meso-dialdehydes 6 and 14 are presented. It was found that both the geometric selectivities and the levels of asymmetric induction...

  2. Rationalization of Product Selectivities in Asymmetric Horner-Wadsworth-Emmons Reactions by Use of a New Method for Transition-State Modeling

    DEFF Research Database (Denmark)

    Norrby, Per-Ola; Brandt, Peter; Rein, Tobias

    1999-01-01

    A new method for creating a transition-state force field, based on quantum chemical normal-mode analysis, is described. The force field was used to rationalize the experimentally observed product selectivities in asymmetric Horner-Wadsworth-Emmons reactions between some chiral phosphonates and ch...

  3. Asymmetric Horner-Wadsworth-Emmons Reactions with meso-Dialdehydes: Scope, Mechanism, and Synthetic Applications

    DEFF Research Database (Denmark)

    Rein, Tobias; Vares, Lauri; Kawasaki, Ikuo

    1999-01-01

    Asymmetric Homer-Wadsworth-Emmons reactions between chiral phosphonate reagents and various meso-dialdehydes have been investigated. A mechanistic model useful for rationalizing the experimentally observed stereoselectivities is presented. Furthermore; strategies for applying these reactions to t...

  4. 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

    2001-01-01

    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...... reactions with carbon, nitrogen, and oxygen nucleophiles. In this latter step, the respective (E) and (Z) alkene substrate isomers were observed to react with opposite stereospecificity: the (E) alkene reacted with retention and the (Z) alkene with inversion of stereochemistry with respect to both...... the allylic stereocenter and the alkene geometry. Thus, a single $gamma@-substituted ester was obtained as the overall product, in high isomeric purity. The method was applied to a synthesis of a subunit of the iejimalides, a group of cytotoxic macrolides....

  5. 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

    2001-01-01

    reactions with carbon, nitrogen, and oxygen nucleophiles. In this latter step, the respective (E) and (Z) alkene substrate isomers were observed to react with opposite stereospecificity: the (E) alkene reacted with retention and the (Z) alkene with inversion of stereochemistry with respect to both...

  6. Parallel Kinetic Resolution of Racemic Aldehydes by Use of Asymmetric Horner-Wadsworth-Emmons Reactions

    DEFF Research Database (Denmark)

    Pedersen, Torben Møller; Jensen, Jakob Feldthusen; Humble, Rikke Eva

    2000-01-01

    A racemic aldehyde can undergo parallel kinetic resolution (PKR) by simultaneous reaction with two different chiral phosphonates, differing either in the structure of the chiral auxiliary or in the structure of the phosphoryl group (i.e., one (E)- and one (Z)-selective reagent). This strategy all...

  7. A Quantum Chemical Exploration of the Horner-Wadsworth-Emmons Reaction

    DEFF Research Database (Denmark)

    Brandt, Peter; Norrby, Per-Ola; Martin, Ivar

    1998-01-01

    The mechanism of the Horner-Wadsworth-Emmons (HWE) reaction has been investigated using high level quantum mechanical calculations on a realistic model system. The solvation contribution has been evaluated using the PCM/DIR method. In the free, anionic system, the rate determining step was found...... effects that could rationalize experimentally observed trends for (E)/(Z)-selectivities have been identified....

  8. Synthetic Applications of Asymmetric Horner-Wadsworth-Emmons Condensations: Approaches to Marine Natural Products

    DEFF Research Database (Denmark)

    Tullis, Joshua S.; Helquist, Paul; Rein, Tobias

    1999-01-01

    Asymmetric HWE condensations of meso-dialdehyde 1 with chiral phosphonates containing 8-phenylmenthol very directly generate chiral moieties that are seen in a number of cytotoxic natural products. The HWE reactions proceed in good yields with synthetically useful geometric and diastereoselectivi...

  9. Versatile Stereocontrol in Asymmetric Horner-Wadsworth-Emmons Resolution of a Racemic Diphenylphosphoryl-Protected a-Aminoaldehyde

    DEFF Research Database (Denmark)

    Kreuder, Reinhard; Rein, Tobias; Reiser, Oliver

    1997-01-01

    In kinetic resolutions of the racemic aldehyde 1 by reaction with chiral phosphonates of type 2, all of which contain the same chiral auxiliary in the same enantiomeric form, any of the four diastereomers 3a, 3b, 4a or 4b can be obtained as the main product by an appropriate choice of reaction pa...

  10. Synthesis of pyrazole containing α-amino acids via a highly regioselective condensation/aza-Michael reaction of β-aryl α,β-unsaturated ketones

    NARCIS (Netherlands)

    Gilfillan, Lynne; Artschwager, Raik; Harkiss, Alexander H.; Liskamp, Rob M J; Sutherland, Andrew

    2015-01-01

    A synthetic approach for the preparation of a new class of highly conjugated unnatural α-amino acids bearing a 5-arylpyrazole side-chain has been developed. Horner-Wadsworth-Emmons reaction of an aspartic acid derived β-keto phosphonate ester with a range of aromatic aldehydes gave β-aryl α,β-unsatu

  11. An efficient procedure based on a MW-assisted Horner-Wadsworth-Emmons reaction for the synthesis of (Z)-3,3-trisubstituted-alpha,beta-unsaturated esters.

    Science.gov (United States)

    Rossi, Daniela; Baraglia, Anna Carnevale; Serra, Massimo; Azzolina, Ornella; Collina, Simona

    2010-08-27

    A microwave-assisted HWE olefination process of readily accessible aryl-alkyl ketones has been developed to provide a rapid access to (Z)-3,3-trisubstituted-alpha,beta-unsaturated methyl esters, key building blocks for the synthesis of biologically active compounds.

  12. Asymmetric synthesis of vinylogous β-amino acids and their incorporation into mixed backbone oligomers.

    Science.gov (United States)

    Wu, Hao; An, Hongchan; Mo, Shuting Cynthia; Kodadek, Thomas

    2017-03-27

    Chiral vinylogous β-amino acids (VBAA) were synthesized using enantioselective Mannich reactions of aldehydes with in situ generated N-carbamoyl imines followed by a Horner-Wadsworth-Emmons reaction. The efficiency with which these units could be incorporated into oligomers with different moieties on the C- and N-terminal sides was established, as was the feasibility of sequencing oligomers containing VBAAs by tandem mass spectrometry. The data show that VBAAs will be useful building blocks for the construction of combinatorial libraries of peptidomimetic compounds.

  13. New modification of the Perkow reaction: halocarboxylate anions as leaving groups in 3-acyloxyquinoline-2,4(1H,3H)-dione compounds

    Science.gov (United States)

    Paleta, Oldřich; Pomeisl, Karel; Kafka, Stanislav; Klásek, Antonín; Kubelka, Vladislav

    2005-01-01

    Substituted 3-(fluoroacyloxy)quinoline-2,4(1H,3H)-diones including 3-(fluoroiodoacetoxy) derivatives react with triethyl phosphite to afford either the product of the Perkow reaction or the corresponding 4-ethoxyquinolin-2(1H)-one. In both reactions, the fluorocarboxylate anion acts as the first observed leaving group. This observation restricts the application of the intramolecular Horner-Wadsworth-Emmons synthesis to modify quinoline-2,4(1H,3H)-diones by the annulation of fluorinated but-2-enolide rings. PMID:16551375

  14. New modification of the Perkow reaction: halocarboxylate anions as leaving groups in 3-acyloxyquinoline-2,4(1H,3H-dione compounds

    Directory of Open Access Journals (Sweden)

    Klásek Antonín

    2005-12-01

    Full Text Available Abstract Substituted 3-(fluoroacyloxyquinoline-2,4(1H,3H-diones including 3-(fluoroiodoacetoxy derivatives react with triethyl phosphite to afford either the product of the Perkow reaction or the corresponding 4-ethoxyquinolin-2(1H-one. In both reactions, the fluorocarboxylate anion acts as the first observed leaving group. This observation restricts the application of the intramolecular Horner-Wadsworth-Emmons synthesis to modify quinoline-2,4(1H,3H-diones by the annulation of fluorinated but-2-enolide rings.

  15. Proline catalyzed α-aminoxylation reaction in the synthesis of biologically active compounds.

    Science.gov (United States)

    Kumar, Pradeep; Dwivedi, Namrata

    2013-02-19

    The search for new and efficient ways to synthesize optically pure compounds is an active area of research in organic synthesis. Asymmetric catalysis provides a practical, cost-effective, and efficient method to create a variety of complex natural products containing multiple stereocenters. In recent years, chemists have become more interested in using small organic molecules to catalyze organic reactions. As a result, organocatalysis has emerged both as a promising strategy and as an alternative to catalysis with expensive proteins or toxic metals. One of the most successful and widely studied secondary amine-based organocatalysts is proline. This small molecule can catalyze numerous reactions such as the aldol, Mannich, Michael addition, Robinson annulation, Diels-Alder, α-functionalization, α-amination, and α-aminoxylation reactions. Catalytic and enantioselective α-oxygenation of carbonyl compounds is an important reaction to access a variety of useful building blocks for bioactive molecules. Proline catalyzed α-aminoxylation using nitrosobenzene as oxygen source, followed by in situ reduction, gives enantiomerically pure 1,2-diol. This molecule can then undergo a variety of organic reactions. In addition, proline organocatalysis provides access to an assortment of biologically active natural products including mevinoline (a cholesterol lowering drug), tetrahydrolipstatin (an antiobesity drug), R(+)-α-lipoic acid, and bovidic acid. In this Account, we present an iterative organocatalytic approach to synthesize both syn- and anti-1,3-polyols, both enantio- and stereoselectively. This method is primarily based on proline-catalyzed sequential α-aminoxylation and Horner-Wadsworth-Emmons (HWE) olefination of aldehyde to give a γ-hydroxy ester. In addition, we briefly illustrate the broad application of our recently developed strategy for 1,3-polyols, which serve as valuable, enantiopure building blocks for polyketides and other structurally diverse and

  16. Synthetic studies on maitotoxin. 1. Stereoselective synthesis of the C'D'E'F'-ring system having a side chain.

    Science.gov (United States)

    Morita, Masayuki; Ishiyama, Seishi; Koshino, Hiroyuki; Nakata, Tadashi

    2008-05-01

    The stereoselective synthesis of the maitotoxin C'D'E'F'-ring system having a side chain has been accomplished through a convergent strategy. The key reactions include Horner-Wadsworth-Emmons coupling of the C'D'E'-ring and the side chain and subsequent construction of the F'-ring by silane reduction of dihydropyran.

  17. Synthesis, Structure and Fluorescence Properties of 5,17-Distyryl-25,26,27,28-tetraproproxycalix[4]arenes in the Cone Conformation

    DEFF Research Database (Denmark)

    Larsen, Mogens; Krebs, Frederik C; Jørgensen, Mikkel

    1998-01-01

    The HWE (Horner-Wadsworth-Emmons) reaction performed on the easily obtainable 5,17-diformyl- calix[4]arenes (cone) with arylmethyl phosphorus ylides yielded 5,17-distyryl-25,26,27, 28-tetrapropoxycalix[4]arenes (cone) in high yield and purely in the E/E configuration. Compounds 2-5 were prepared...

  18. Total synthesis of aquatolide

    NARCIS (Netherlands)

    Saya, J.M.; Vos, K.; Klein Nijenhuis, R.A.; van Maarseveen, J.H.; Ingemann, S.; Hiemstra, H.

    2015-01-01

    A total synthesis of the sesquiterpene lactone aquatolide has been accomplished. The central step is an intramolecular [2 + 2]-photocycloaddition of an allene onto an alpha,beta-unsaturated delta-lactone. Other key steps are an intramolecular Horner-Wadsworth-Emmons reaction to close the lactone and

  19. Syntheses of New Functionalized Monomers for π-Conjugated Polymers

    Institute of Scientific and Technical Information of China (English)

    D.VYPRACHTICKY; V.CIMRO; P.PAVLKOVA; I.KMNEK

    2007-01-01

    1 Results Tailored monomers based on the activated esters of 2,5-dibromobenzoic (sulfonic) acid derivatives, the 3-substituted 2,5-dibromothiophenes, the 9-substituted 2,7-dibromocarbazoles, and on the brominated 1,10-phenanthrolines suitable for Suzuki, Yamamoto or Grignard metathesis (GRIM) coupling reactions were synthesized and characterized by melting point, elemental analysis, 1H NMR, FTIR and TLC. The Horner-Wadsworth-Emmons reaction mechanism was utilized for the preparation of the 3-[2-(pyren-1...

  20. A novel and efficient route for the preparation of atorvastatin

    Institute of Scientific and Technical Information of China (English)

    Jian Gao; Yang Hui Guo; Ya Ping Wang; Xiang Jing Wang; Wen Sheng Xiang

    2011-01-01

    A novel and efficient synthetic method of atorvastatin was described. The key step of the synthesis was the construction of the olefin linkage between the chiral side chain and skeleton via a Horner-Wadsworth-Emmons reaction, resulting in the advanced intermediate of atorvastatin under hydrogenation of the olefin over Pd/C. This novel method is more useful for the practical synthesis of atorvastatin than its document reported methods.

  1. Ferrocene-Based Monomers, Oligomers and Polymers as Electro-Active Materials

    OpenAIRE

    Al Khalyfeh, Khaled

    2016-01-01

    The present PhD thesis deals with the synthesis and characterization of functionalized ferrocenes with up to four aldehyde and vinyl groups and their usage as monomers to produce novel ferrocene-based oligomers with conjugated backbones via ADMET (acyclic diene metathesis) and HWE (Horner-Wadsworth-Emmons) reaction protocols. In addition, ferrocene-containing polymers (linear, cross-linked and co-polymers) with aliphatic backbones generated by anionic bulk and solution polymerization routes, ...

  2. The application of green chemistry methods in organophosphorus synthesis

    Science.gov (United States)

    Odinets, Irina L.; Matveeva, E. V.

    2012-03-01

    Data concerning the synthesis of organophosphorus compounds in ionic liquids, in water and under solvent-free conditions are considered and summarized. It is shown that this strategy, which complies with the definition of green chemistry, has advantages in terms of the rate of the process and the yields of target products as compared with syntheses in common organic solvents. The Wittig, Horner-Wadsworth-Emmons, Kabachnik-Fields, Arbuzov and Michaelis reactions are considered as examples. The bibliography includes 178 references.

  3. Synthesis, Structure and Fluorescence Properties of 5,17-Distyryl-25,26,27,28-tetraproproxycalix[4]arenes in the Cone Conformation

    DEFF Research Database (Denmark)

    Larsen, Mogens; Krebs, Frederik C; Jørgensen, Mikkel

    1998-01-01

    The HWE (Horner-Wadsworth-Emmons) reaction performed on the easily obtainable 5,17-diformyl- calix[4]arenes (cone) with arylmethyl phosphorus ylides yielded 5,17-distyryl-25,26,27, 28-tetrapropoxycalix[4]arenes (cone) in high yield and purely in the E/E configuration. Compounds 2-5 were prepared ...... and fluorescence spectroscopy and compared to the monomeric fluorophore, 3,5-dimethyl-4-propoxy-(E)-stilbene (10)....

  4. Design, synthesis and biological evaluation of a simplified fluorescently labeled discodermolide as a molecular probe to study the binding of discodermolide to tubulin.

    Science.gov (United States)

    Qi, Jun; Blanden, Adam R; Bane, Susan; Kingston, David G I

    2011-09-01

    The design, synthesis, and biological evaluation of a simplified fluorescently labeled discodermolide analogue possessing a dimethylaminobenzoyl fluorophore has been achieved. Stereoselective Suzuki coupling and Horner-Wadsworth-Emmons reaction comprised the key tactics for its construction. The analogue exhibited qualitatively similar activity to paclitaxel in a tubulin assembly assay, and it can thus be used as a fluorescent molecular probe to explore the local environment of the discodermolide binding site on tubulin. The results of fluorescence measurements on the tubulin-bound analogue are reported.

  5. 天然产物Longistylin A,Longistylin C和Cajanotone的全合成%Total Synthesis of Longistylin A, Longistylin C and Cajanotone

    Institute of Scientific and Technical Information of China (English)

    陈文章; 王聪; 樊玲玲; 王建塔; 岳炜洲; 汤磊

    2015-01-01

    Natural products longistylin A, longistylin C and cajanotone belong to stilbenes family and exhibit varieties of bioactivities. Using Horner-Wadsworth-Emmons (HWE) and 1,3-sigma rearrangement reactions as key steps, longistylin A and longistylin C have been successfully synthesized in six steps from 3,5-dimethoxy benzoic acid. Besides, using Barbier and 1,3-sigma rearrangement reactions as key steps, cajanotone has been first prepared in eight steps from 3,5-dihydroxy benzoic acid.%天然产物Longistylin A, Longistylin C和Cajanotone属于茋类化合物,具有广泛的生物活性.以3,5-二甲氧基苯甲酸为原料,以 Horner-Wadsworth-Emmons (HWE)反应和1,3-sigma重排反应为关键步骤,经6步反应同时得到了Longistylin A和Longistylin C.采用3,5-二羟基苯甲酸为原料,以Barbier反应和1,3-sigma重排反应为关键步骤,经8步反应全合成得到了Cajanotone.

  6. The Catalytic Asymmetric Intramolecular Stetter Reaction.

    Science.gov (United States)

    de Alaniz, Javier Read; Rovis, Tomislav

    2009-05-01

    This account chronicles our efforts at the development of a catalytic asymmetric Stetter reaction using chiral triazolium salts as small molecule organic catalysts. Advances in the mechanistically related azolium-catalyzed asymmetric benzoin reaction are discussed, particularly as they apply to catalyst design. A chronological treatise of reaction discovery, catalyst optimization and reactivity extension follows.

  7. Asymmetric reactions in continuous flow

    Directory of Open Access Journals (Sweden)

    Xiao Yin Mak

    2009-04-01

    Full Text Available An overview of asymmetric synthesis in continuous flow and microreactors is presented in this review. Applications of homogeneous and heterogeneous asymmetric catalysis as well as biocatalysis in flow are discussed.

  8. Relative stereochemical determination and synthesis of the C17-C25 δ-lactone fragment of hemicalide.

    Science.gov (United States)

    Fleury, Etienne; Sorin, Geoffroy; Prost, Elise; Pancrazi, Ange; Sautel, François; Massiot, Georges; Lannou, Marie-Isabelle; Ardisson, Janick

    2013-02-01

    Hemicalide is a novel marine metabolite polyketide distinguished by a unique mechanism of action. Because of insufficient quantities of purified material, this natural product has evaded complete stereochemical assignments. Recently, we have determined the relative stereochemistry of the C8-C13 hexad by synthesizing the C1-C13 fragment. Presently, we report the assignment of the C17-C25 δ-lactone fragment. NMR analysis of authentic hemicalide along with a computational conformation study allowed us to reduce the number of putative relative isomers from 16 to 4. Concise syntheses of the four candidate diastereomers were achieved using a common strategy based on a Dias aldehyde allylation reaction, an intramolecular Horner-Wadsworth-Emmons olefination, and a dihydroxylation reaction. Finally, thorough NMR comparisons enabled us to deduce the relative stereochemistry of the C1-C17 fragment with high certainty.

  9. Preparation and Characterization of (E)- and (Z)-2-(Biphenyl-4-yl)-1-(4-bromophenyl)-1-phenylethene Isomers

    Energy Technology Data Exchange (ETDEWEB)

    Son, Hojun; Lee, Dongwoo; Lee, Taewon; Ok, Kangmin; Park, Kwangyong [Chung-Ang Univ., Seoul (Korea, Republic of)

    2014-06-15

    Stilbene compounds, well known for their biological activities, have been widely investigated as short subunits of poly(p-phenylenevinylene), the first light-emitting polymer, to understand the emission mechanism and relationship between the molecular structure and emitted light. Distyrylarylene derivatives are also well known as blue fluorescent materials and hole-transport materials. As part of our program directed toward the development of novel blue electroluminescent materials with unsymmetrical stilbene or distyrylarylene skeletons, we have prepared various bromostilbene intermediates by the Horner. Wadsworth.Emmons reaction of bromobenzophenone derivatives with benzyl phosphonates. However, great difficulties arise when isolating and identifying pure products from these reactions because of the generation of chromatographically inseparable mixtures of (E)- and (Z)-geometric isomers. Therefore, an efficient process for separating the two isomers is quite necessary for the systematic development of electroluminescent π-conjugated hydrocarbons.

  10. The Challenge of Synthesizing Oligomers for Molecular Wires

    Directory of Open Access Journals (Sweden)

    Frederik C. Krebs

    2011-02-01

    Full Text Available Controlling the size of the oligomer and introducing functional groups at the ends of the oligomer that allow it to react with separate electrodes are critical issues when preparing materials for molecular wires. We demonstrate a general synthetic approach to oligophenylenevinylene (OPV derivative molecules with a molecular length up to 9–10 nm which allow for the introduction of aromatic thioacetate functionality in fully conjugated oligomer systems. Oligomers containing 3–15 phenyl units were synthesized by step wise Horner-Wadsworth-Emmons (HWE reactions of a bifunctional OPV-monomer, which demonstrated good control of the size of the OPVs. Workup after each reaction step ensures a high purity of the final products. End group functionalization was introduced as a last step.

  11. 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

    2012-01-01

    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.

  12. [Development of new methods in asymmetric reactions and their applications].

    Science.gov (United States)

    Node, Manabu

    2002-01-01

    Several novel methods using chiral reagents and biocatalysts for asymmetric reactions are described. Among those reactions, asymmetric reduction via a novel tandem Michael addition/Meerwein-Ponndorf-Verley reduction of acyclic alpha,beta-unsaturated ketones using a chiral mercapto alcohol, asymmetric synthesis of allene-1,3-dicarboxylate via crystallization induced asymmetric transformation, and improved asymmetric nitroolefination of lactones and lactames at alpha-carbon using new chiral reagents were developed. In the reactions using biocatalysts, asymmetric dealkoxycarbonylation of bicyclic beta-keto diesters having sigma-symmetry with lipase or esterase to give optically active beta-keto esters, the asymmetric reduction of bicyclic 1,3-diketones having sigma-symmetry with Baker's yeast to give optically active keto alcohols, and the asymmetric aldol reaction of glycine with threonine aldolase were also developed. The above mentioned products were effectively utilized as chiral building blocks for the asymmetric synthesis of natural products and drugs.

  13. Catalytic asymmetric umpolung reactions of imines

    Science.gov (United States)

    Wu, Yongwei; Hu, Lin; Li, Zhe; Deng, Li

    2015-07-01

    The carbon-nitrogen double bonds in imines are fundamentally important functional groups in organic chemistry. This is largely due to the fact that imines act as electrophiles towards carbon nucleophiles in reactions that form carbon-carbon bonds, thereby serving as one of the most widely used precursors for the formation of amines in both synthetic and biosynthetic settings. If the carbon atom of the imine could be rendered electron-rich, the imine could react as a nucleophile instead of as an electrophile. Such a reversal in the electronic characteristics of the imine functionality would facilitate the development of new chemical transformations that convert imines into amines via carbon-carbon bond-forming reactions with carbon electrophiles, thereby creating new opportunities for the efficient synthesis of amines. The development of asymmetric umpolung reactions of imines (in which the imines act as nucleophiles) remains uncharted territory, in spite of the far-reaching impact such reactions would have in organic synthesis. Here we report the discovery and development of new chiral phase-transfer catalysts that promote the highly efficient asymmetric umpolung reactions of imines with the carbon electrophile enals. These catalysts mediate the deprotonation of imines and direct the 2-azaallyl anions thus formed to react with enals in a highly chemoselective, regioselective, diastereoselective and enantioselective fashion. The reaction tolerates a broad range of imines and enals, and can be carried out in high yield with as little as 0.01 mole per cent catalyst with a moisture- and air-tolerant operational protocol. These umpolung reactions provide a conceptually new and practical approach to chiral amino compounds.

  14. Synthesis of 6E-Geranylgeraniol-19-oic Acid

    Institute of Scientific and Technical Information of China (English)

    LI Shu-hua; PENG Li-Zeng; LI Wei-dong; LI Yu-lin

    2003-01-01

    The present paper deals with the facile synthesis of 6E-geranylgeraniol-19-oic acid(1), a naturally occuring alicyclic diterpene acid, by a Horner-Wadsworth-Emmons olefination of two readily available fragments 7 and 3.

  15. Asymmetric H-D exchange reactions of fluorinated aromatic ketones

    KAUST Repository

    Zhao, Yujun

    2012-01-01

    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.

  16. Asymmetric chemical reactions by polarized quantum beams

    Science.gov (United States)

    Takahashi, Jun-Ichi; Kobayashi, Kensei

    One of the most attractive hypothesis for the origin of homochirality in terrestrial bio-organic compounds (L-amino acid and D-sugar dominant) is nominated as "Cosmic Scenario"; a chiral impulse from asymmetric excitation sources in space triggered asymmetric reactions on the surfaces of such space materials as meteorites or interstellar dusts prior to the existence of terrestrial life. 1) Effective asymmetric excitation sources in space are proposed as polarized quantum beams, such as circularly polarized light and spin polarized electrons. Circularly polarized light is emitted as synchrotron radiation from tightly captured electrons by intense magnetic field around neutron stars. In this case, either left-or right-handed polarized light can be observed depending on the direction of observation. On the other hand, spin polarized electrons is emitted as beta-ray in beta decay from radioactive nuclei or neutron fireballs in supernova explosion. 2) The spin of beta-ray electrons is longitudinally polarized due to parity non-conservation in the weak interaction. The helicity (the the projection of the spin onto the direction of kinetic momentum) of beta-ray electrons is universally negative (left-handed). For the purpose of verifying the asymmetric structure emergence in bio-organic compounds by polarized quantum beams, we are now carrying out laboratory simulations using circularly polarized light from synchrotron radiation facility or spin polarized electron beam from beta-ray radiation source. 3,4) The target samples are solid film or aqueous solution of racemic amino acids. 1) K.Kobayashi, K.Kaneko, J.Takahashi, Y.Takano, in Astrobiology: from simple molecules to primitive life; Ed. V.Basiuk; American Scientific Publisher: Valencia, 2008. 2) G.A.Gusev, T.Saito, V.A.Tsarev, A.V.Uryson, Origins Life Evol. Biosphere. 37, 259 (2007). 3) J.Takahashi, H.Shinojima, M.Seyama, Y.Ueno, T.Kaneko, K.Kobayashi, H.Mita, M.Adachi, M.Hosaka, M.Katoh, Int. J. Mol. Sci. 10, 3044

  17. Asymmetric Catalytic Reactions Catalyzed by Chiral Titanium Complexes

    Institute of Scientific and Technical Information of China (English)

    FENG XiaoMing

    2001-01-01

    @@ Chiral titanium complexes is very importance catalyst to asymmetric catalytic reactions. A series of catalytic systems based on titanium-chiral ligands complexes has been reported. This presentation will discuss some of our recent progress on asymmetric catalytic reactions catalyzed by chiral titanium complexes.

  18. Asymmetric Catalytic Reactions Catalyzed by Chiral Titanium Complexes

    Institute of Scientific and Technical Information of China (English)

    FENG; XiaoMing

    2001-01-01

    Chiral titanium complexes is very importance catalyst to asymmetric catalytic reactions. A series of catalytic systems based on titanium-chiral ligands complexes has been reported. This presentation will discuss some of our recent progress on asymmetric catalytic reactions catalyzed by chiral titanium complexes.  ……

  19. 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: ldias@iqm.unicamp.br [Universidade de Campinas (UNICAMP), SP (Brazil). Inst. de Quimica

    2012-12-15

    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)

  20. Recent advances in copper-catalyzed asymmetric coupling reactions

    Directory of Open Access Journals (Sweden)

    Fengtao Zhou

    2015-12-01

    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.

  1. Developing a Practical Chiral Toolbox for Asymmetric Catalytic Reactions

    Institute of Scientific and Technical Information of China (English)

    ZHANG XuMu

    2001-01-01

    @@ Chiral Quest's Toolbox Approach: During the last several decades, chemists have made major progress in discovering man-made catalysts to perform challenging asymmetric transformations. However, there is no universal chiral ligand or catalyst for solving problems in enantioselective transformations. The focus of Chiral Quest's research is to develop a useful chiral toolbox for strategically important asymmetric catalytic reactions by inventing a diverse set of novel chiral ligands and combining them with transition metals as effective enantioselective catalysts. The toolbox approach addresses significant problems in organic stereochemistry and has resulted in practical methods for the synthesis of chiral pharmaceuticals and agrochemicals

  2. Developing a Practical Chiral Toolbox for Asymmetric Catalytic Reactions

    Institute of Scientific and Technical Information of China (English)

    ZHANG; XuMu

    2001-01-01

    Chiral Quest's Toolbox Approach: During the last several decades, chemists have made major progress in discovering man-made catalysts to perform challenging asymmetric transformations. However, there is no universal chiral ligand or catalyst for solving problems in enantioselective transformations. The focus of Chiral Quest's research is to develop a useful chiral toolbox for strategically important asymmetric catalytic reactions by inventing a diverse set of novel chiral ligands and combining them with transition metals as effective enantioselective catalysts. The toolbox approach addresses significant problems in organic stereochemistry and has resulted in practical methods for the synthesis of chiral pharmaceuticals and agrochemicals  ……

  3. Rhodium catalyzed asymmetric Pauson-Khand reaction using SDP ligands

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    The activity and enantiocontrol ability of the chiral catalysts prepared from spiro diphosphine ligands, SDP, and rhodium precursor were investigated in the asymmetric catalytic Pauson-Khand reaction. The results showed that SDP ligands were very effective in Rh-catalyzed Pauson-Khand reaction, and their complexes with rhodium could convert a variety of 1,6-enyne compounds into bicyclopentone derivatives under CO atmosphere in high yields with good enantioselectivities. The SbF6- was found to be a suitable counter anion of the catalyst, and 1,2-dichloroethane was the best choice of the solvent for Pauson-Khand reaction.

  4. Axially chiral imidodiphosphoric Acid catalyst for asymmetric sulfoxidation reaction: insights on asymmetric induction.

    Science.gov (United States)

    Jindal, Garima; Sunoj, Raghavan B

    2014-04-22

    Insights into chiral induction for an asymmetric sulfoxidation reaction involving a single oxygen atom transfer are gained through analyzing the stereocontrolling transition states. The fitting of the substrate into the chiral cavity of a new class of imidodiphosphoric Brønsted acids, as well as weak CH⋅⋅⋅π and CH⋅⋅⋅O noncovalent interactions, are identified as responsible for the observed chiral induction.

  5. Asymmetric Organocatalytic Reactions of α,β-Unsaturated Cyclic Ketones

    Directory of Open Access Journals (Sweden)

    Giuseppe Bartoli

    2011-03-01

    Full Text Available The 1,4-conjugate addition of nucleophiles to α,β-unsaturated carbonyl compounds represents one fundamental bond-forming reaction in organic synthesis. The development of effective organocatalysts for the enantioselective conjugate addition of malonate, nitroalkane and other carbon and heteroatom nucleophiles to cycloenones constitutes an important research field and has been explored in recent years. At the same time, asymmetric Diels-Alder reactions have been developed and often a mechanism has been demonstrated to be a double addition rather than synchronous. This review aims to cover literature up to the end of 2010, describing all the different organocatalytic asymmetric 1,4-conjugate additions even if they are listed as transfer hydrogenation, cycloadditions or desymmetrization of aromatic compounds.

  6. Asymmetric Aldol Reaction Catalyzed by Modularly Designed Organocatalysts

    Institute of Scientific and Technical Information of China (English)

    Sinha, Debarshi; Mandal, Tanmay; Gogoi, Sanjib; Goldman, Joshua J.; 赵从贵

    2012-01-01

    The self-assembly of the precatalyst modules, which are amino acids and cinchona alkaloid derivatives, leads to the direct formation of the desired organocatalysts without any synthesis. These modularly designed organocatalysts (MDOs) may be used for catalyzed asymmetric aldol reaction the corresponding aldol products may be obtained in mediocre diastereoselectivities (up to 79 : 21 dr). Depending on structure of the aldehyde substrates, to excellent ee values (up to 92% ee) with moderate

  7. Asymmetric Stetter reactions catalyzed by thiamine diphosphate-dependent enzymes.

    Science.gov (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

    2014-12-01

    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.

  8. Asymmetric induction in the zirconium catalyzed ethylmagnesiation reaction

    Energy Technology Data Exchange (ETDEWEB)

    Bell, J.L.; Whitby, R.J.; Jones, R.V.H. [Univ. of Southampton, Hants (United Kingdom)

    1995-12-31

    In 1985 Dzhemilev reported the zirconium catalysed ethylmagnesiation of terminal alkenes. A chiral centre is formed during the reaction which occurs under mild conditions. The authors have applied this reaction to a number of substrates and a mechanism has been elucidated. In order to induce asymmetry into the reaction, several chiral literature catalysts were synthesised including Ethylenebis(tetrahydroindenyl)zirconium dichloride and two more hindered complexes reported by Erker. All of these catalysts displayed low activity and poor asymmetric induction with terminal alkenes. The synthesis and properties of two novel catalysts will be described. Results show high activity furnishing carbomagnesiated products in excellent yields with as little as 2 mol% catalyst. The enantiomeric excesses induced by the complexes are as high as 79% with terminal alkenes but are >95% with cyclic ethers. The catalyst has proved recoverable. Ethylmagnesiation of an amine followed by an acidic workup furnishes the chiral complex in a quantitative return.

  9. Direct Catalytic Asymmetric Mannich-Type Reaction of Alkylamides.

    Science.gov (United States)

    Arteaga, Fernando Arteaga; Liu, Zijian; Brewitz, Lennart; Chen, Jianyang; Sun, Bo; Kumagai, Naoya; Shibasaki, Masakatsu

    2016-05-20

    Direct enolate formation coupled with subsequent enantioselective C-C bond formation remains a topic of intense interest in asymmetric catalysis. This methodology is achieved even with low acidic amides without an electron-withdrawing group at the α-position in the context of a Mannich-type reaction. Acetate-, propionate-, and butyrate-type 7-azaindoline amides served as enolate precursors to afford the desired Mannich adducts with high stereoselectivity, and ligand-enabled diastereo-divergency provided access to both anti/syn diastereomers. The facile transformation of the amide moiety ensures the synthetic utility of the Mannich adducts.

  10. Direct asymmetric aldol reactions catalyzed by lipase from porcine pancreas.

    Science.gov (United States)

    Zheng, Jing; Xie, Bang-Hua; Chen, Yan-Li; Cao, Jian-Fei; Yang, Yang; Guan, Zhi; He, Yan-Hong

    2014-01-01

    Porcine pancreas lipase type II (PPL II) exhibited unnatural catalytic activity in direct asymmetric aldol reactions between cyclic ketones and aromatic or heteroaromatic aldehydes in acetonitrile in the presence of phosphate buffer. A wide range of substrates was accepted by the enzyme to afford the corresponding aldol products in low to high yields (10-98%), with moderate to excellent enantioselectivities (53-94% ee, for anti-isomers) and low to moderate diastereoselectivities (48/52-87/13 dr, anti/syn). This methodology expands the application of PPL II, and it might be developed into a potentially valuable method for sustainable organic synthesis.

  11. Computational Studies on Cinchona Alkaloid-Catalyzed Asymmetric Organic Reactions.

    Science.gov (United States)

    Tanriver, Gamze; Dedeoglu, Burcu; Catak, Saron; Aviyente, Viktorya

    2016-06-21

    Remarkable progress in the area of asymmetric organocatalysis has been achieved in the last decades. Cinchona alkaloids and their derivatives have emerged as powerful organocatalysts owing to their reactivities leading to high enantioselectivities. The widespread usage of cinchona alkaloids has been attributed to their nontoxicity, ease of use, stability, cost effectiveness, recyclability, and practical utilization in industry. The presence of tunable functional groups enables cinchona alkaloids to catalyze a broad range of reactions. Excellent experimental studies have extensively contributed to this field, and highly selective reactions were catalyzed by cinchona alkaloids and their derivatives. Computational modeling has helped elucidate the mechanistic aspects of cinchona alkaloid catalyzed reactions as well as the origins of the selectivity they induce. These studies have complemented experimental work for the design of more efficient catalysts. This Account presents recent computational studies on cinchona alkaloid catalyzed organic reactions and the theoretical rationalizations behind their effectiveness and ability to induce selectivity. Valuable efforts to investigate the mechanisms of reactions catalyzed by cinchona alkaloids and the key aspects of the catalytic activity of cinchona alkaloids in reactions ranging from pharmaceutical to industrial applications are summarized. Quantum mechanics, particularly density functional theory (DFT), and molecular mechanics, including ONIOM, were used to rationalize experimental findings by providing mechanistic insights into reaction mechanisms. B3LYP with modest basis sets has been used in most of the studies; nonetheless, the energetics have been corrected with higher basis sets as well as functionals parametrized to include dispersion M05-2X, M06-2X, and M06-L and functionals with dispersion corrections. Since cinchona alkaloids catalyze reactions by forming complexes with substrates via hydrogen bonds and long

  12. Reactivity of allenylphosphonates and allenylphosphine oxides toward 9-chloroacridines and acridone- A facile route to new -substituted acridones

    Indian Academy of Sciences (India)

    A Leela Siva Kumari; Venu Srinivas; K C Kumara Swamy

    2013-11-01

    Base-mediated addition of acridones to allenylphosphonates/allenylphosphine oxides (OCH2CMe2CH2O)P(O)CH=C=CR1R2 {R1 = R2 = Me (1), R1 = R2 = [−CH2−]5 (2)}, Ph2P(O)C(H)=C=CR1R2 {R1 = R2 = Me (3), R1 = R2 = [−CH2−]5 (4)} and (EtO)2P(O)C(H)=C=CMe2 (5) in DMF results in the regiospecific formation of phosphono-acridones and acridonylphosphine oxides. The acridone addition products were also obtained in the reaction of allenes 1 and 2 with 9-chloroacridine under [Pd]-catalysed conditions, along with (unexpected) -acridinyl substituted allenes. In contrast, 9-benzyl-6-chloro-purine reacted with 1 affording a -substituted purinone phosphonate. Allenes 1-2 did not react with acridones in the absence of base (CsF), but in the presence of Pd(OAc)2/DMF (or DMA)/pivalic acid rearranged to give 1,3-butadienes probably via [Pd]-allyl complexes. The phosphono-acridones were amenable to Horner-Wadsworth-Emmons (HWE) reaction and led to -substituted acridones. Key products have been characterized by single-crystal X-ray crystallography.

  13. BF3 x Et2O-mediated cascade cyclizations: synthesis of schweinfurthins F and G.

    Science.gov (United States)

    Mente, Nolan R; Neighbors, Jeffrey D; Wiemer, David F

    2008-10-17

    The total synthesis of the natural stilbene (+)-schweinfurthin G (8) has been accomplished through a sequence based on an efficient cationic cascade cyclization. This cascade process is initiated by Lewis acid promoted ring opening of an epoxide and terminated through a novel reaction with a phenolic oxygen "protected" as its MOM ether. Several Lewis acids have been examined for their ability to induce this new reaction, and BF3 x Et2O was found to be the most effective. The only major byproduct under these conditions was one where the expected secondary alcohol was found as its MOM ether derivative (e.g., 30). While this byproduct could be converted to the original target compound through hydrolysis, it also could be employed as a protected alcohol to allow preparation of a benzylic phosphonate (43) without dehydration of the secondary alcohol. The resulting phosphonate was employed in a Horner-Wadsworth-Emmons condensation with an aldehyde representing the right half of the target compounds, an approach complementary to previous studies based on condensation of a right-half phosphonate and a left-half aldehyde.

  14. Catalytic Asymmetric Carbon-Carbon Forming Reactions Catalyzed Chiral Schiff Base-Metal Complexes

    Institute of Scientific and Technical Information of China (English)

    Takanori; Tanaka; Masahiko; Hayashi

    2007-01-01

    1 Results In 1991, we disclosed the novel asymmetric catalysts prepared from chiral Schiff base and titanium alkoxide in the reaction of asymmetric silylcyanation of aldehydes (eq.1)[1]. Since our first report, chiral Schiff base-metal complex was proven to be efficient in a variety of asymmetric reactions. We reported the first example of enantioselective addition of diketene to aldehydes promoted by chiral Schiff base-titanium alkoxide complexes (eq.2)[2]. The products of this reaction have been cove...

  15. Direct asymmetric aldol reaction using MBHA resin-supported peptide containing L-proline unit

    Institute of Scientific and Technical Information of China (English)

    Liang Zhang; Wen Bo Ding; Yong Ping Yu; Hong Bin Zou

    2009-01-01

    MBHA resin-supported tripeptide catalyst system containing L-proline unit has been developed for use in the direct asymmetric aldol reaction of acetone and aldehydes,which afford the corresponding products with satisfactory isolated yields and enantiomeric excesses.

  16. Catalytic Asymmetric Nitro-Mannich Reactions with a Yb/K Heterobimetallic Catalyst

    Directory of Open Access Journals (Sweden)

    Tatsuya Nitabaru

    2010-03-01

    Full Text Available A catalytic asymmetric nitro-Mannich (aza-Henry reaction with rare earth metal/alkali metal heterobimetallic catalysts is described. A Yb/K heterobimetallic catalyst assembled by an amide-based ligand promoted the asymmetric nitro-Mannich reaction to afford enantioenriched anti-b-nitroamines in up to 86% ee. Facile reduction of the nitro functionality allowed for efficient access to optically active 1,2-diamines.

  17. Rhodium-catalyzed Asymmetric Ring Opening Reaction of Oxabenzo-norbornadiene with Substituted Phenolic Nucleophiles

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    We have developed an asymmetric ring opening reaction of oxabenzonorbornadienes with substituted phenolic nucleophiles. Under the reaction conditions ( [Rh(COD)Cl]2 (1 mol%),(S)-(R)-PPF-ptBu2 (2 mol%), THF, reflux), the reaction products were obtained with high yield and enantiomeric excesses ( up to 99% ee).

  18. Preparation and Reactions of Amino Acid Ester Sulfones as New Remote Asymmetrical Induced Reagents

    Institute of Scientific and Technical Information of China (English)

    ZHOU,Cheng-He; BAI,Xue; LI,Tan-Qing; WU,Jun; Alfred Hassner

    2004-01-01

    @@ The development of chiral auxiliary-controlled asymmetric synthesis has been receiving increasing interest in recent yearsfi,2] Various chiral auxiliary reagents have been observed[3] and a lot of results showed that variation of the chiral auxiliary could influence asymmetric induction. Recently, it has been reported the reaction of the aminated sulfones as a remote chiral auxiliary with α,β-unsaturated carbonyl compounds.[4] Here we would like to report the preparation of amino acid ester sulfones as new remote asymmetrical induced reagents and their reactions with α,β-unsaturated esters.

  19. Asymmetric Friedel-Crafts Reaction of Indoles with Imines by an Organic Catalyst

    Science.gov (United States)

    Wang, Yong-Qiang; Song, Jun; Hong, Ran; Li, Hongming; Deng, Li

    2011-01-01

    In this communication, we report an asymmetric Friedel-Crafts reaction of indoles with imines catalyzed by a bifunctional cinchona alkaloid catalyst. This is the first efficient organocatalytic asymmetric Friedel-Crafts reaction of indoles with imines. This reaction is operationally simple and, unprecedently, affords high enantioselectivity for a wide range of indoles and both aryl and alkyl imines. This establishes a direct, convergent and versatile approach to optically active 3-indolyl-methanamines, a structural motif embedded in numerous indole alkaloids and synthetic indole derivatives. PMID:16787078

  20. The First Catalytic Asymmetric Morita-Baylis-Hillman Reaction of Acrolein with Aromatic Aldehydes

    Institute of Scientific and Technical Information of China (English)

    曾兴平; 刘运林; 计从斌; 周剑

    2012-01-01

    We report the first example of catalytic asymmetric Morita-Baylis-Hillman reaction of acrolein with aromatic aldehydes. The use of 10 mol% of Hatakeyama's catalyst β-isocupreidine C4, in combination with 20 mol% of 2,6-dimethoxybenzoic acid, could catalyze the reaction to give the desired products in up to 81% ee.

  1. Asymmetric Hydrogenation of α-Hydroxy Ketones: A Reaction Sensitive toward Electronic Effect of Substrates

    Institute of Scientific and Technical Information of China (English)

    XU Hui; MENG Qing-Hua; ZHANG Zhao-Guo

    2008-01-01

    An efficient asymmetric hydrogenation of a-hydroxy ketones was reported with the catalyst prepared from [RuCl2(benzene)]2 and SunPhos,chiral terminal 1,2-diols were obtained in up to 99% ee.This Ru-catalyzed asymmetric hydrogenation reaction of a-hydroxy ketones represents a new route for the synthesis of chiral terminal 1,2-diols.

  2. Monofunctional primary amine: A new class of organocatalyst for asymmetric Aldol reaction

    Indian Academy of Sciences (India)

    KHIANGTE VANLALDINPUIA; PORAG BORA; GHANASHYAM BEZ

    2017-03-01

    A new class of organocatalysts involving a primary amine as the only functional group is developed for catalytic asymmetric aldol reaction of cyclohexanone/ cyclopentanone with various aryl aldehydes in thepresence of benzoic acid as an additive at −10◦C. In an unexpected observation, the primary amine catalyzed reactions gave excellent yield and good to excellent stereoselectivity, while secondary amines were found to have little or no reactivity under similar reaction conditions.

  3. Direct Asymmetric Aldol Type Reaction with Ethyl Diazoacetate: Stereoselective Synthesis of α, β-Dihydroxy Esters

    Institute of Scientific and Technical Information of China (English)

    LIAO Ming-Yi; YAO Wen-Gang; FENG Hai-Tao; WANG Jian-Bo

    2003-01-01

    @@ Enantioselective aldol condensation under catalytic condition remains a challenging task in modern organic synthesis, and numerous efforts have been directed to this area. In particular, the direct catalytic asymmetric aldol reaction is very attractive considering the requirement of atom efficiency. This has been studied only recently, and several very practical processes have been developed. We have recently initiated a study on the direct asymmetric aldol type reaction with ethyl diazoacetate as nucleophile. Moderate enantioselectivities (65% ~91% ee ) were achieved in the condensation of aldehydes with ethyl diazoacetate catalyzed by the chiral complex of BINOL derivatives-Zr (OBu- t )4. [1

  4. Multicomponent asymmetric reactions mediated by proline lithium salt

    DEFF Research Database (Denmark)

    Renzi, Polyssena; Overgaard, Jacob; Bella, Marco

    2010-01-01

    The multicomponent reaction between proline lithium salt, 2-cyclohexen-1-one and aliphatic aldehydes affords the 4- alkylidene-2-cyclohexen-1-ones, which are interesting fragrances, and bicyclic amino acids that bear four additional stereocenters, obtained as single stereoisomer....

  5. Asymmetric hydrogenation with highly active IndolPhos-Rh catalysts: kinetics and reaction mechanism

    NARCIS (Netherlands)

    Wassenaar, J.; Kuil, M.; Lutz, M.; Spek, A.L.; Reek, J.N.H.

    2010-01-01

    The mechanism of the IndolPhos-Rh-catalyzed asymmetric hydrogenation of prochiral olefins has been investigated by means of X-ray crystal structure determination, kinetic measurements, high-pressure NMR spectroscopy, and DFT calculations. The mechanistic study indicates that the reaction follows an

  6. Chitosan aerogel: a recyclable, heterogeneous organocatalyst for the asymmetric direct aldol reaction in water.

    Science.gov (United States)

    Ricci, Alfredo; Bernardi, Luca; Gioia, Claudio; Vierucci, Simone; Robitzer, Mike; Quignard, Françoise

    2010-09-14

    Aerogel microspheres of chitosan, an abundant biopolymer obtained from marine crustaceans, have been successfully applied to catalyze the asymmetric aldol reaction in water, providing the products in high yields and with good stereoselectivity (up to 93% ee) and recyclability (up to 4 runs). Yields were favourably affected by additives such as DNP and stearic acid.

  7. Asymmetric hydrogenation with highly active IndolPhos-Rh catalysts: kinetics and reaction mechanism

    NARCIS (Netherlands)

    Wassenaar, J.; Kuil, M.; Lutz, M.; Spek, A.L.; Reek, J.N.H.

    2010-01-01

    The mechanism of the Indol- Phos–Rh-catalyzed asymmetric hydrogenation of prochiral olefins has been investigated by means of X-ray crystal structure determination, kinetic measurements, high-pressure NMR spectroscopy, and DFT calculations. The mechanistic study indicates that the reaction follows a

  8. Asymmetric hydrogenation with highly active IndolPhos-Rh catalysts: kinetics and reaction mechanism

    NARCIS (Netherlands)

    Wassenaar, J.; Kuil, M.; Lutz, M.; Spek, A.L.; Reek, J.N.H.

    2010-01-01

    The mechanism of the IndolPhos-Rh-catalyzed asymmetric hydrogenation of prochiral olefins has been investigated by means of X-ray crystal structure determination, kinetic measurements, high-pressure NMR spectroscopy, and DFT calculations. The mechanistic study indicates that the reaction follows an

  9. Copper-catalyzed asymmetric allylic substitution reactions with organozinc and Grignard reagents

    NARCIS (Netherlands)

    Geurts, Koen; Fletcher, Stephen P.; van Zijl, Anthoni W.; Minnaard, Adriaan J.; Feringa, Ben L.; Bignall, H. E.; Jauncey, D. L.; Lovell, J. E. J.; Tzioumis, A. K.; Kedziora-Chudczer, L. L.; MacQuart, J. P.; Tingay, S. J.; Rayner, D. P.; Clay, R. W.

    2008-01-01

    Asymmetric allylic alkylations (AAAs) are among the most powerful C-C bond-forming reactions. We present a brief overview of copper-catalyzed AAAs with organometallic reagents and discuss our own contributions to this field. Work with zinc reagents and phosphoramidite ligands provided a framework fo

  10. Measurements of Dynamical Dipole in isospin asymmetric fusion reactions

    Science.gov (United States)

    Giaz, A.; Corsi, A.; Camera, F.; Bracco, A.; Crespi, F. C. L.; Leoni, S.; Nicolini, R.; Vandone, V.; Benzoni, G.; Blasi, N.; Brambilla, S.; Million, B.; Wieland, O.; Cinausero, M.; Degelier, M.; Gramegna, F.; Kravchuk, V. L.; Marchi, T.; Rizzi, V.; Bardelli, L.; Barlini, S.; Bini, M.; Carboni, S.; Casini, G.; Chiari, M.; Nannini, A.; Pasquali, G.; Piantelli, S.; Poggi, G.; Baiocco, G.; Bruno, M.; D'agostino, M.; Morelli, L.; Vannini, V.; Colonna, M.; Di Toro, M.; Rizzo, C.; Bednarcyk, P.; Ciemala, M.; Kmiecik, M.; Maj, A.; Mazurek, K.; Menczynski, W.; Alba, R.; Maiolino, C.; Santonocito, D.; Montanari, D.; Ordine, A.

    2012-05-01

    In heavy ion nuclear reactions the process leading to complete fusion is expected to produce pre-equilibrium γ-ray emission, if particular conditions are met. Indeed, when there is an N/Z asymmetry between projectile and target, charge equilibration takes place with a collective dipole oscillation, called Dynamical Dipole (DD), associated to a γ-ray emission. The existing experimental data concerning this pre-equilibrium γ-ray emission are still rather scarce and manly concentrated in the A≊132 mass region. The very preliminary results concerning the measurement of the DD γ-ray emission in the fusion reaction 16O (Elab=192 MeV) + 116Sn at 12 MeV/u will be presented and compared with the γ yield measured for the same reaction at 8.1 and 15.6 MeV/u. The present experiment aims at the measurement of the total emission yield of the DD at 12 MeV/u where the predicted theoretical yield does not completely reproduce the experimental data. The experiment has been performed at the INFN Legnaro Laboratories using the GARFIELD-HECTOR array.

  11. Iridium-catalyzed asymmetric ring-opening reactions of oxabicyclic alkenes with secondary amine nucleophiles

    Directory of Open Access Journals (Sweden)

    Dingqiao Yang

    2009-10-01

    Full Text Available Iridium-catalyzed asymmetric ring-opening reactions of oxabicyclic alkenes with various aliphatic and aromatic secondary amines are reported for the first time. The reaction gave the corresponding trans-1,2-dihydronaphthalenol derivatives in good yields with moderate enantioselectivities in the presence of 2.5 mol % [Ir(CODCl]2 and 5 mol % bisphosphine ligand (S-p-Tol-BINAP. The trans-configuration of 3f was confirmed by X-ray crystallography.

  12. Zinc-prolinamide complex catalyzed direct asymmetric aldol reactions in the presence of water

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    An efficient direct asymmetric aldol reaction with zinc triflate and prolinamides as combined catalysts is reported.A series of chiral prolinamides have been designed and used in the direct aldol reaction resulting in the desired products with excellent yields(up to 94% yield) and high enantioselectivities(up to 96% ee).Water was found to play a significant role in the formation of the aldol products,which suggests a new strategy in the design of new organic catalysts.

  13. Chiral amide from (1, 2)-(+)-norephedrine and furoic acid: An efficient catalyst for asymmetric Reformatsky reaction

    Indian Academy of Sciences (India)

    Nallamuthu Ananthi; Sivan Velmathi

    2014-01-01

    Chiral amide derived from (1, 2)-(+)-norephedrine and 2-furoic acid was found to catalyse the asymmetric Reformatsky reaction between prochiral aldehydes and α-bromo ethylacetate with diethylzinc as zinc source. The corresponding chiral -hydroxy esters were formed in 99% yield with over 80% enantiomeric excess. The presence of air was found to be essential for the effective C-C bond formation. The mechanism for the catalytic reaction was proposed.

  14. High-Throughput Screening of the Asymmetric Decarboxylative Alkylation Reaction of Enolate-Stabilized Enol Carbonates

    KAUST Repository

    Stoltz, Brian

    2010-06-14

    The use of high-throughput screening allowed for the optimization of reaction conditions for the palladium-catalyzed asymmetric decarboxylative alkylation reaction of enolate-stabilized enol carbonates. Changing to a non-polar reaction solvent and to an electron-deficient PHOX derivative as ligand from our standard reaction conditions improved the enantioselectivity for the alkylation of a ketal-protected,1,3-diketone-derived enol carbonate from 28% ee to 84% ee. Similar improvements in enantioselectivity were seen for a β-keto-ester derived- and an α-phenyl cyclohexanone-derived enol carbonate.

  15. High-Throughput Screening of the Asymmetric Decarboxylative Alkylation Reaction of Enolate-Stabilized Enol Carbonates.

    Science.gov (United States)

    McDougal, Nolan T; Virgil, Scott C; Stoltz, Brian M

    2010-01-01

    The use of high-throughput screening allowed for the optimization of reaction conditions for the palladium-catalyzed asymmetric decarboxylative alkylation reaction of enolate-stabilized enol carbonates. Changing to a non-polar reaction solvent and to an electron-deficient PHOX derivative as ligand from our standard reaction conditions improved the enantioselectivity for the alkylation of a ketal-protected,1,3-diketone-derived enol carbonate from 28% ee to 84% ee. Similar improvements in enantioselectivity were seen for a β-keto-ester derived- and an α-phenyl cyclohexanone-derived enol carbonate.

  16. Rational design of cyclopropane-based chiral PHOX ligands for intermolecular asymmetric Heck reaction

    Directory of Open Access Journals (Sweden)

    Marina Rubina

    2014-07-01

    Full Text Available A novel class of chiral phosphanyl-oxazoline (PHOX ligands with a conformationally rigid cyclopropyl backbone was synthesized and tested in the intermolecular asymmetric Heck reaction. Mechanistic modelling and crystallographic studies were used to predict the optimal ligand structure and helped to design a very efficient and highly selective catalytic system. Employment of the optimized ligands in the asymmetric arylation of cyclic olefins allowed for achieving high enantioselectivities and significantly suppressing product isomerization. Factors affecting the selectivity and the rate of the isomerization were identified. It was shown that the nature of this isomerization is different from that demonstrated previously using chiral diphosphine ligands.

  17. Synthesis and Catalytic Asymmetric Reaction of Chiral Pyridine Prolinol Derivatives

    Institute of Scientific and Technical Information of China (English)

    CHEN Xiao; ZHANG Yong-Xin; DU Da-Ming; HUA Wen-Ting

    2003-01-01

    @@ The enantioselective reduction of prochiral ketones with borane in the presence of a chiral ligand leading to enantiomerically pure secondary alcohols has received considerable attention in recent years. [1] Enantiomerically pure secondary alcohols are important intermediates for the synthesis of various other organic compounds such as halides, esters, ethers, ketones and amines. To the best of our knowledge, the use of pyridine prolinol derivatives in the reduction of ketones has not been reported so far. Thus, it should be of interest to investigate the catalytic a bility of such ligands. We have an ongoing project in the synthesis and application of chiral pyridine derivatives in chiral molecular recognition[2] and we want to evaluate the effect resulting from the introduction of a pyridinyl moiety onto the catalysts. We expect that the cooperation of pyridine unit and chiral prolinol unit in new ligands may result in unique properties for catalytic reaction.

  18. Isolation of microbe for asymmetric reduction of prochiral aromatic ketone and its reaction characters

    Institute of Scientific and Technical Information of China (English)

    YANG Zhonghua; ZENG Rong; WANG Yu; WANG Guanghui; YAO Shanjing

    2007-01-01

    The favorable microbes for the asymmetric reduction of prochiral aromatic ketones was isolated from soil using acetophenone as the sole carbon source,when the asymmetric reduction of acetophenone (ACP) to chiral α-phenethyl alcohol (PEA) was chosen as the model reaction.Two microbe strains with excellent catalytic activity were obtained.They were Geotrichum candidum and Pichia pastoris identified by bacteria identification.The product of the asymmetric reduction of ACP catalyzed by Pichia pastoris was mainly R-PEA and that by Geotrichum candidum was mainly S-PEA.The yield and enantiomeric excesses (e.e.) could respectively reach 75% and 90% for Pichiapastoris,and 80% and 70% for Geotrichum candidum,much higher than those catalyzed by baker's yeast.

  19. Asymmetric reactions using the chiral imides derived from (S)-glutamic acid

    Energy Technology Data Exchange (ETDEWEB)

    Ikota, N.; Hanaki, A.

    1986-05-01

    The development of a variety of methods for asymmetric induction continue to pose an important challenge to the syntheses of chiral natural products and pharmaceuticals such as prostaglandins and ..beta.. - lactams. In the authors continuing studies on the use of chiral pyroglutamic acid derivatives for the asymmetric reagents and the natural product syntheses, the authors examined the ..cap alpha.., ..beta..-unsaturated carboximide as chiral dienophile in the Diels-Alder reaction and the asymmetric 1, 4- conjugate addition reaction. The requisite ..cap alpha.., ..beta..-unsaturated carboximides (2) were prepared by N-acylation of the chiral 2-pyrrolidone derivative (1) derived from (S)-glutamic acid. 1 was treated with 1 eq. of sodium hydride in tetrahydrofuran (THF), followed by addition of acryloyl chloride and crotonyl chloride to afford the imides (2) in 90-95% yields. Asymmetric Diels-Alder process using these chiral dienophiles was made with cyclopentadiene as the diene. The chiral imides (2, 1 eq.) and cyclopentadiene (10 eq.) were reacted in toluene at -78/sup 0/C to afford the adducts (3) in 60-70% yields. The adducts (3) were converted to the corresponding methyl esters (4) by treatment with sodium methoxide in methanol, then endo- and exo-isomers were separated and the ratio of these isomers was determined by GLC (gas chromatography) analysis. Enantiomeric excess of endo-4 was determined based on the values of optical rotation. The diastereoselectivity was greatly increased by the use of Lewis acid adend such as diethylaluminum chloride.

  20. Asymmetric Electrophilic α-Amination of Silyl Enol Ether Derivatives via the Nitrosocarbonyl Hetero-ene Reaction.

    Science.gov (United States)

    Sandoval, David; Samoshin, Andrey V; Read de Alaniz, Javier

    2015-09-18

    The first example of a general asymmetric nitrosocarbonyl hetero-ene reaction is described. The procedure uses a copper-catalyzed aerobic oxidation of a commercially available chiral nitrosocarbonyl precursor (EleNOr) and is operationally simple. The transformation is both high yielding and highly diastereoselective for a range of silyl enol ether derivatives. A variety of synthetically useful postfunctionalization reactions are presented along with a mechanistic rationale that can be used as a predictive model for future asymmetric reactions with nitrosocarbonyl intermediates.

  1. Violation of the action-reaction principle in an asymmetrically excited system

    CERN Document Server

    Donaire, M

    2016-01-01

    Violation of the action-reaction principle is shown to occur in the van der Waals interaction between two atoms, one of which is excited. It is accompanied by the transfer of linear momentum to the electromagnetic vacuum. The vacuum momentum results from the asymmetric interference of the virtual photons scattered off each atom along the interatomic direction, which is in itself a manifestation of the optical theorem. This momentum, of equal strength and opposite direction to the momentum gained by the two-atom system, is ultimately released through directional spontaneous emission. A quantitative prediction of this phenomenon is made in a two-alkali atom system. It is conjectured that action-reaction violation takes place in any asymmetrically excited system.

  2. Catalytic asymmetric Povarov reaction of isatin-derived 2-azadienes with 3-vinylindoles.

    Science.gov (United States)

    Zhang, Hong-Hao; Sun, Xiao-Xue; Liang, Jing; Wang, Yue-Ming; Zhao, Chang-Chun; Shi, Feng

    2014-12-21

    The first catalytic asymmetric Povarov reaction of isatin-derived 2-azadienes with 3-vinylindoles was established in the presence of chiral phosphoric acid, which tolerates a wide range of substrates with generally excellent diastereoselectivity and good enantioselectivity (up to >95 : 5 dr, 89 : 11 er). This approach will greatly enrich the chemistry of the catalytic asymmetric Povarov reaction, in particular ketone-involved transformations. Furthermore, this protocol represents the first diastereo- and enantio-selective construction of a spiro[indolin-3,2'-quinoline] framework bearing an indole moiety. This novel type of spiro-compound not only contains two chiral centers, including one quaternary stereogenic center, but also integrates two biologically important structures of spiro[indolin-3,2'-quinoline] and indole, which may find medicinal applications after bioassay.

  3. Chiral PEPPSI Complexes: Synthesis, Characterization, and Application in Asymmetric Suzuki–Miyaura Coupling Reactions

    KAUST Repository

    Benhamou, Laure

    2014-01-13

    PEPPSI complexes incorporating chiral N-heterocyclic carbene (NHC) ligands based on 2,2-dimethyl-1-(o-substituted aryl)propan-1-amines were synthesized. Two complexes, with one saturated and one unsaturated NHC ligand, were structurally characterized. The chiral PEPPSI complexes were used in asymmetric Suzuki-Miyaura reactions, giving atropisomeric biaryl products in modest to good enantiomeric ratios. © 2013 American Chemical Society.

  4. Asymmetric Synthesis of Fully Substituted Cyclopentane-Oxindoles through an Organocatalytic Triple Michael Domino Reaction

    Science.gov (United States)

    Zou, Liang-Hua; Philipps, Arne R; Raabe, Gerhard; Enders, Dieter

    2015-01-01

    An efficient, highly stereoselective asymmetric synthesis of fully functionalized cyclopentanes bearing an oxindole moiety and several other functional groups in one pot has been developed. Key step is an organocatalytic triple Michael domino reaction forming three C–C bonds and six stereocenters, including a quaternary one. Starting from equimolar amounts of simple substrates, a high molecular complexity can be reached after a Wittig olefination in one pot. The new protocol can easily be scaled up to gram amounts. PMID:25470781

  5. Novel chiral ionic liquid (CIL) assisted selectivity enhancement to (L)-proline catalyzed asymmetric aldol reactions

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Long; Zhang, Haibo; Luo, Huadong; Zhou, Xiaohai; Cheng, Gongzhen [College of Chemistry, Wuhan University (China)

    2011-09-15

    A significant improvement of the chemical yields (up to 88%), stereoselectivity (> 99:1) and enantiomeric excesses (up to 98%) of (L)-proline catalyzed direct asymmetric aldol reaction was found when proline based chiral ionic liquids (CILs) were added as additives. Different ratios of DMSO/H{sub 2}O as solvent and chiral ionic liquids (CILs) with chiral cations of different chain length were investigated. (author)

  6. Asymmetric Synthesis of Amino-Bis-Pyrazolone Derivatives via an Organocatalytic Mannich Reaction.

    Science.gov (United States)

    Chauhan, Pankaj; Mahajan, Suruchi; Kaya, Uğur; Peuronen, Anssi; Rissanen, Kari; Enders, Dieter

    2017-07-07

    A new series of N-Boc ketimines derived from pyrazolin-5-ones have been used as electrophiles in asymmetric Mannich reactions with pyrazolones. The amino-bis-pyrazolone products are obtained in excellent yields and stereoselectivities by employing a very low loading of 1 mol % of a bifunctional squaramide organocatalyst. Depending on the substitution at position 4 of the pyrazolones, the new protocol allows for the generation of one or two tetrasubstituted stereocenters, including a one-pot version combing the Mannich reaction with a base-mediated halogenation.

  7. Asymmetric catalysis in aqueous media: use of metal-chiral crown ethers as efficient chiral Lewis acid catalysts in asymmetric aldol reactions

    Directory of Open Access Journals (Sweden)

    Shu Kobayashi

    2001-01-01

    Full Text Available Metal-chiral crown ether complexes have been developed as efficient chiral Lewis acid catalysts for asymmetric aldol reactions of silyl enol ethers with aldehydes in aqueous media. While many excellent catalytic asymmetric reactions have been developed recently, most of them have to be carried out under strictly anhydrous conditions in organic solvents. This is probably due to the instability of many catalysts and/or intermediates in the presence of even a small amount of water. To address this issue, we searched for metal-crown ether complexes on the basis of our "multi-coordination" hypothesis, and found that lead(II and lanthanide(III catalysts worked well as chiral Lewis acids in aqueous media. To the best of our knowledge, these are the first examples of chiral crown-based Lewis acids that can be successfully used in catalytic asymmetric reactions. The catalysts have been characterized by X-ray diffraction, and their unique structures as chiral catalysts have been revealed. Use of water as a solvent is essential in these asymmetric catalysis, and the role of water on these reactions to explain the high reactivity and selectivity has been suggested. Another important point is that kinetic studies have shown the possibility that these types of crown ether complexes would be suitable as chiral catalysts employed in aqueous media. In addition, although the catalytic asymmetric aldol reactions are one of the most powerful carbon-carbon bond-forming methodologies and several successful examples have been reported, the use of aprotic anhydrous solvents and low reaction temperatures (-78 °C has been needed in almost all successful cases. On the other hand, the present reactions proceeded smoothly at -10-0 °C in water-alcohol solutions while retaining high levels of diastereo- and enantioselectivities.

  8. The allyl intermediate in regioselective and enantioselective iridium-catalyzed asymmetric allylic substitution reactions.

    Science.gov (United States)

    Madrahimov, Sherzod T; Markovic, Dean; Hartwig, John F

    2009-06-03

    The isolation and structural characterization of metallacyclic allyl (2a) and crotyl (2b) iridium complexes are reported. Complexes 2a and 2b are rare examples of iriduim allyl complexes that undergo nucleophilic attack at terminal position, rather than the central position, of the allyl unit. Structures of 2a and 2b were obtained by X-ray diffraction. Nucleophilic attack was observed at the carbon that is bound to iridium trans to phosphorus through a longer Ir-C bond. However, the effect of the trans phosphine ligand on the Ir-C bond lengths was smaller than the effect of the substituent on the allyl group in 2b. The competence of complexes 2a and 2b to be intermediates in the catalytic asymmetric allylic substitutions was evaluated by studying their reactivity toward stabilized carbon and heteroatom nucleophiles and comparing the rates and selectivities to those of the catalytic reactions. The stereoselectivity and regioselectivity of stoichiometric reactions of 2b were similar to those of reactions catalyzed by the previously reported iridium catalysts, supporting their intermediacy in the catalytic reactions. On the basis of the structural data, a model is proposed for the origin of stereoselectivity in iridium-catalyzed asymmetric allylic substitution reactions.

  9. Synthesis of Novel Chiral Dibenzo [ a, c ] cycloheptadiene Bis(oxazoline) and Catalytic Asymmetric Reactions

    Institute of Scientific and Technical Information of China (English)

    FU Bin; DU Da-Ming; WANG Jian-Bo

    2003-01-01

    @@ Over the last decade, C2-symmetric chiral oxazoline metal complexes have been recognized as an effective classof chiral catalyst in a variety of transition metal catalyzed asymmetric reactions. [1] High catalytic activities and enantiomeric excesses have been obtained using C2-symmetric chiral ligands in conjunction with suitable transition metal ion, for example, the hydrosilylation of ketone, allylic alkylation, Michael addition, Diels-Alder cycloaddition, and cyclopropanation. Thus, the design and synthesis of new chiral oxazoline ligands have inspired many scientists to work with great efforts.

  10. Asymmetric Cooperative Catalysis in a Three-Component Reaction: Mechanism and Origin of Enantio- and Diastereoselectivities.

    Science.gov (United States)

    Kisan, Hemanta K; Sunoj, Raghavan B

    2016-08-05

    Mechanistic insights gained through density functional theory (DFT M06 and B3LYP) computations on a three-component cooperative asymmetric catalytic reaction between a diazo ester, a carbamate, and an imine, catalyzed by dirhodium acetate and chiral phosphoric acid (Brønsted acid), are presented. The addition of the dirhodium-bound enol to the imine yielding an α,β-diamino ester is energetically more preferred over a potentially competitive protonation of the same enol leading to an α-amino ester.

  11. Asymmetric synthesis of fully substituted cyclopentane-oxindoles through an organocatalytic triple Michael domino reaction.

    Science.gov (United States)

    Zou, Liang-Hua; Philipps, Arne R; Raabe, Gerhard; Enders, Dieter

    2015-01-12

    An efficient, highly stereoselective asymmetric synthesis of fully functionalized cyclopentanes bearing an oxindole moiety and several other functional groups in one pot has been developed. Key step is an organocatalytic triple Michael domino reaction forming three C-C bonds and six stereocenters, including a quaternary one. Starting from equimolar amounts of simple substrates, a high molecular complexity can be reached after a Wittig olefination in one pot. The new protocol can easily be scaled up to gram amounts. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Progress of Chiral Schiff Bases with C1 Symmetry in Metal-Catalyzed Asymmetric Reactions.

    Science.gov (United States)

    Hayashi, Masahiko

    2016-12-01

    In this Personal Account, various chiral Schiff base-metal-catalyzed enantioselective organic reactions are reported; the Schiff bases used were O,N,O- as well as N,N,P-tridentate ligands and N,N-bidentate ligands having C1 symmetry. In particular, the enantioselective addition of trimethylsilyl cyanide, dialkylzinc, and organozinc halides to aldehydes, enantioselective 1,4-addition of dialkylzinc to cyclic and acyclic enones, and asymmetric allylic oxidation are reported. Typically, ketimine-type Schiff base-metal complexes exhibited higher reactivity and enantioselectivity compared with the corresponding aldimine-type Schiff base-metal complexes. Notably, remarkable ligand acceleration was observed for all reactions. The obtained products can be used as key intermediates for optically active natural products and pharmaceuticals.

  13. Total synthesis of (+)-geldanamycin and (-)-o-quinogeldanamycin: asymmetric glycolate aldol reactions and biological evaluation.

    Science.gov (United States)

    Andrus, Merritt B; Meredith, Erik L; Hicken, Erik J; Simmons, Bryon L; Glancey, Russell R; Ma, Wei

    2003-10-17

    The total synthesis of (+)-geldanamycin (GA), following a linear route, has been completed using a demethylative quinone-forming reaction as the last step. Key steps include the use of two new asymmetric boron glycolate aldol reactions. To set the anti-C11,12 hydroxymethoxy functionality, (S,S)-5,6-bis-4-methoxyphenyldioxanone 8 was used. Methylglycolate derived from norephedrine 5 set the C6,7 methoxyurethane stereochemistry. The quinone formation step using nitric acid gave the non-natural o-quino-GA product 55 10:1 over geldanamycin. Other known oxidants gave an unusual azaquinone product 49. o-Quino-GA 55 binds Hsp90 with good affinity but is less cytotoxic compared to GA.

  14. Synthetic studies on hemicalide: development of a convergent approach toward the C1-C25 fragment.

    Science.gov (United States)

    Sorin, Geoffroy; Fleury, Etienne; Tran, Christine; Prost, Elise; Molinier, Nicolas; Sautel, François; Massiot, Georges; Specklin, Simon; Meyer, Christophe; Cossy, Janine; Lannou, Marie-Isabelle; Ardisson, Janick

    2013-09-20

    Synthetic studies on hemicalide, a recently isolated marine natural product displaying highly potent antiproliferative activity and a unique mode of action, have highlighted a reliable Horner-Wadsworth-Emmons olefination to create the C6-C7 alkene and a remarkable efficient Suzuki-Miyaura coupling to form the C15-C16 bond, resulting in the development of a convergent approach toward the C1-C25 fragment.

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

    Directory of Open Access Journals (Sweden)

    Adi Wolfson

    2013-03-01

    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.

  16. Chiral Borated Esters in Asymmetric Synthesis:1.The First Asymmetric Reaction Catalyzed by Chiral Spiroborated Esters with an O3BN Framework

    Institute of Scientific and Technical Information of China (English)

    LIU, De-Jun(刘德军); SHAN, Zi-Xing(单自兴); QIN, Jin-Gui(秦金贵)

    2004-01-01

    The first asymmetric reaction catalyzed by chiral spiroborated esters with an O3BN framework was reported. In the presence of 0.1 equivalent of (R,S)-1 or (S,S)-1, acetophenone was reduced by 0.6 equivalent of borane in THF at 0-5 ℃ for 2 h to give (R)-1-phenylethanol of up to 76% ee and 73% isolated yield. Influence of reaction conditions on the stereoselectivity of the reduction was investigated and a possible catalytic mechanism of the chiral spiroborated esters toward the reduction was also suggested.

  17. Rational design of catalysts for asymmetric diamination reaction using transition state modeling.

    Science.gov (United States)

    Jindal, Garima; Sunoj, Raghavan B

    2014-05-07

    The stereoselective synthesis of 1,2-diamines has remained a formidable challenge. A recent palladium-catalyzed asymmetric diamination of conjugated double bonds using di-tert-butyldiaziridinone appears promising. The axially chiral binol phosphoramidite ligands are successful in offering high enantioselectivity. The density functional theory investigations revealed that the energies of the stereocontrolling transition states for the C-N bond formation depend on a number of weak non-covalent interactions such as C-H···π, C-H···O and anagostic interactions. We envisaged that the modulation in these interactions in the transition states, through subtle changes in chiral phosphoramidite substituents, could be exploited toward steering the stereoselectivity. The effect of systematic modifications on both 3,3' positions of the binol as well as on the amido nitrogen on the stereochemical outcome is predicted. It is identified that high enantioselectivity requires a balance between the nature of the substituents on binol and amido groups. The reduced size of the amido substituents demands increased bulk on the binol whereas lowering the size on the binol demands increased bulk on the amido for higher stereoselectivity. The substituent at the α-position of the amido group is found to be vital and appears to be a hot spot for modifications. These insights derived from studies on the stereocontrolling transition states could help improve the catalytic efficacies in palladium-catalyzed asymmetric diamination reactions.

  18. Transition state models for probing stereoinduction in Evans chiral auxiliary-based asymmetric aldol reactions.

    Science.gov (United States)

    Shinisha, C B; Sunoj, Raghavan B

    2010-09-08

    The use of chiral auxiliaries is one of the most fundamental protocols employed in asymmetric synthesis. In the present study, stereoselectivity-determining factors in a chiral auxiliary-based asymmetric aldol reaction promoted by TiCl(4) are investigated by using density functional theory methods. The aldol reaction between chiral titanium enolate [derived from Evans propionyl oxazolidinone (1a) and its variants oxazolidinethione (1b) and thiazolidinethione (1c)] and benzaldehyde is examined by using transition-state modeling. Different stereochemical possibilities for the addition of titanium enolates to aldehyde are compared. On the basis of the coordination of the carbonyl/thiocarbonyl group of the chiral auxiliary with titanium, both pathways involving nonchelated and chelated transition states (TSs) are considered. The computed relative energies of the stereoselectivity-determining C-C bond formation TSs in the nonchelated pathway, for both 1a and 1c, indicate a preference toward Evans syn aldol product. The presence of a ring carbonyl or thiocarbonyl group in the chiral auxiliary renders the formation of neutral TiCl(3)-enolate, which otherwise is energetically less favored as compared to the anionic TiCl(4)-enolate. Hence, under suitable conditions, the reaction between titanium enolate and aldehyde is expected to be viable through chelated TSs leading to the selective formation of non-Evans syn aldol product. Experimentally known high stereoselectivity toward Evans syn aldol product is effectively rationalized by using the larger energy differences between the corresponding diastereomeric TSs. In both chelated and nonchelated pathways, the attack by the less hindered face of the enolate on aldehyde through a chair-like TS with an equatorial disposition of the aldehydic substituent is identified as the preferred mode. The steric hindrance offered by the isopropyl group and the possible chelation are identified as the key reasons behind the interesting

  19. Excitation of the dynamical dipole in the charge asymmetric reaction 16O + 116Sn

    Science.gov (United States)

    Corsi, A.; Wieland, O.; Kravchuk, V. L.; Bracco, A.; Camera, F.; Benzoni, G.; Blasi, N.; Brambilla, S.; Crespi, F. C. L.; Giussani, A.; Leoni, S.; Million, B.; Montanari, D.; Moroni, A.; Gramegna, F.; Lanchais, A.; Mastinu, P.; Brekiesz, M.; Kmiecik, M.; Maj, A.; Bruno, M.; D'Agostino, M.; Geraci, E.; Vannini, G.; Barlini, S.; Casini, G.; Chiari, M.; Nannini, A.; Ordine, A.; Di Toro, M.; Rizzo, C.; Colonna, M.; Baran, V.

    2009-08-01

    The γ-ray emission from the dynamical dipole formed in heavy-ion collisions during the process leading to fusion was measured for the N/Z asymmetric reaction 16O + 116Sn at beam energies of 8.1 and 15.6 MeV/nucleon. High-energy γ-rays and charged particles were measured in coincidence with the heavy recoiling residual nuclei. The data are compared with those from the N/Z symmetric reaction 64Ni + 68Zn at bombarding energies of 4.7 and 7.8 MeV/nucleon, leading to the same CN with the same excitation energies as calculated from kinematics. The measured yield of the high-energy γ-rays from the 16O-induced reaction is found to exceed that of the thermalized CN and the excess yield increases with bombarding energy. The data are in rather good agreement with the predictions for the dynamical dipole emission based on the Boltzmann-Nordheim-Vlasov model. In addition, a comparison with existing data in the same mass region is performed to extract information on the dipole moment dependence.

  20. Excitation of the dynamical dipole in the charge asymmetric reaction {sup 16}O + {sup 116}Sn

    Energy Technology Data Exchange (ETDEWEB)

    Corsi, A. [Dipartimento di Fisica, Universita di Milano, Milano (Italy); INFN Sezione di Milano, Milano (Italy); Wieland, O. [INFN Sezione di Milano, Milano (Italy); Kravchuk, V.L. [Laboratori Nazionali INFN di Legnaro, Legnaro (Italy); Bracco, A. [Dipartimento di Fisica, Universita di Milano, Milano (Italy); INFN Sezione di Milano, Milano (Italy); Camera, F. [Dipartimento di Fisica, Universita di Milano, Milano (Italy); INFN Sezione di Milano, Milano (Italy)], E-mail: franco.camera@mi.infn.it; Benzoni, G.; Blasi, N.; Brambilla, S. [INFN Sezione di Milano, Milano (Italy); Crespi, F.C.L.; Giussani, A.; Leoni, S. [Dipartimento di Fisica, Universita di Milano, Milano (Italy); INFN Sezione di Milano, Milano (Italy); Million, B. [INFN Sezione di Milano, Milano (Italy); Montanari, D.; Moroni, A. [Dipartimento di Fisica, Universita di Milano, Milano (Italy); INFN Sezione di Milano, Milano (Italy); Gramegna, F.; Lanchais, A.; Mastinu, P. [Laboratori Nazionali INFN di Legnaro, Legnaro (Italy); Brekiesz, M.; Kmiecik, M.; Maj, A. [Niewodniczanski Institute of Nuclear Physics, Polish Academy of Sciences, Krakow (Poland)] (and others)

    2009-08-24

    The {gamma}-ray emission from the dynamical dipole formed in heavy-ion collisions during the process leading to fusion was measured for the N/Z asymmetric reaction {sup 16}O + {sup 116}Sn at beam energies of 8.1 and 15.6 MeV/nucleon. High-energy {gamma}-rays and charged particles were measured in coincidence with the heavy recoiling residual nuclei. The data are compared with those from the N/Z symmetric reaction {sup 64}Ni + {sup 68}Zn at bombarding energies of 4.7 and 7.8 MeV/nucleon, leading to the same CN with the same excitation energies as calculated from kinematics. The measured yield of the high-energy {gamma}-rays from the {sup 16}O-induced reaction is found to exceed that of the thermalized CN and the excess yield increases with bombarding energy. The data are in rather good agreement with the predictions for the dynamical dipole emission based on the Boltzmann-Nordheim-Vlasov model. In addition, a comparison with existing data in the same mass region is performed to extract information on the dipole moment dependence.

  1. An overview on the applications of `Doyle catalysts’ in asymmetric cyclopropanation, cyclopropenation and C-H insertion reactions

    Indian Academy of Sciences (India)

    Thomas J Colacot

    2000-06-01

    The chiral dirhodium(II) carboxamidates are a unique class of chiral catalysts useful for asymmetric inter- and intramolecular cyclopropanation, cyclopropenation and C-H insertion reactions with excellent enantioselectivities. The broad applications of these catalysts in organic syntheses are briefly reviewed.

  2. Asymmetric three-component domino reaction: an original access to chiral nonracemic 1,3-thiazin-2-ones.

    Science.gov (United States)

    Peudru, Flavie; Le Cavelier, Fabien; Lohier, Jean-François; Gulea, Mihaela; Reboul, Vincent

    2013-11-15

    A new asymmetric three-component domino process, based on a diastereoselective hetero-Diels-Alder reaction, involving an aldehyde, an alkene, and a chiral thiocarbamate was developed. The chiral auxiliary is directly removed during this process, leading to enantioenriched 2H-1,3-thiazin-2-ones with up to 96% ee.

  3. Non-cross-linked polystyrene-supported 2-imidazolidinone chiral auxiliary: synthesis and application in asymmetric alkylation reactions

    Science.gov (United States)

    Nguyen, Quynh Pham Bao

    2013-01-01

    Summary Asymmetric alkylation reactions using non-cross-linked polystyrene (NCPS)-supported 2-imidazolidinone chiral auxiliaries were successfully investigated with excellent diastereocontrol (>99% de). The recovery and the recycling of this soluble polymer-supported chiral auxiliary were achieved in order to produce highly optical pure carboxylic acids. PMID:24204423

  4. Deciphering the origin of cooperative catalysis by dirhodium acetate and chiral spiro phosphoric acid in an asymmetric amination reaction.

    Science.gov (United States)

    Kisan, Hemanta K; Sunoj, Raghavan B

    2014-12-04

    The mechanism of asymmetric amination of diazo-acetate by tert-butyl carbamate catalyzed by dirhodium tetra(trifluoro)acetate and chiral SPINOL-phosphoric acid is examined using DFT (M06 and B3LYP) computations. A cooperative participation of both catalysts is noticed in the stereo-controlling transition state of the reaction.

  5. Synthesis of novel chiral tridentate Schiff-base ligands and their applications in catalytic asymmetric Henry reaction.

    Science.gov (United States)

    Qiang, Gen-Rong; Shen, Tian-Hua; Zhou, Xiao-Cong; An, Xiao-Xia; Song, Qing-Bao

    2014-12-01

    A series of chiral tridentate Schiff-bases were prepared and used as ligands in the catalytic asymmetric Henry reaction. Under the optimal conditions, a variety of arylaldehydes were smoothly converted into corresponding adducts with high yields (up to 98%) and excellent enantioselectivities (up to 97% ee).

  6. Metal-ligand binding affinity vs reactivity: qualitative studies in Rh(I)-catalyzed asymmetric ring-opening reactions.

    Science.gov (United States)

    Tsui, Gavin Chit; Dougan, Patrick; Lautens, Mark

    2013-06-01

    Rh(I)-catalyzed asymmetric ring opening (ARO) of oxabenzonorbornadiene is used as a model system to qualitatively study reactions involving multiple metal-ligand interactions. The key feature of this approach is the use of product ee as an indicator to quickly gain important information such as the relative ligand binding affinity and relative reactivity of catalysts.

  7. Design and synthesis of bistereogenic chiral ionic liquids and their use as solvents for asymmetric Baylis-Hillman reactions.

    Science.gov (United States)

    Garre, Satish; Parker, Erica; Ni, Bukuo; Headley, Allan D

    2008-09-07

    Three novel chiral ionic liquids (CILs) containing two chiral centers in the side chain bonded to the 2-position of the imidazolium cation and different anions have been synthesized, characterized and used as chiral solvents for asymmetric Baylis-Hillman (BH) reactions; good yields and fair enantioselectivities were obtained.

  8. Dynamics of reaction-diffusion patterns controlled by asymmetric nonlocal coupling as a limiting case of differential advection.

    Science.gov (United States)

    Siebert, Julien; Alonso, Sergio; Bär, Markus; Schöll, Eckehard

    2014-05-01

    A one-component bistable reaction-diffusion system with asymmetric nonlocal coupling is derived as a limiting case of a two-component activator-inhibitor reaction-diffusion model with differential advection. The effects of asymmetric nonlocal couplings in such a bistable reaction-diffusion system are then compared to the previously studied case of a system with symmetric nonlocal coupling. We carry out a linear stability analysis of the spatially homogeneous steady states of the model and numerical simulations of the model to show how the asymmetric nonlocal coupling controls and alters the steady states and the front dynamics in the system. In a second step, a third fast reaction-diffusion equation is included which induces the formation of more complex patterns. A linear stability analysis predicts traveling waves for asymmetric nonlocal coupling, in contrast to a stationary Turing patterns for a system with symmetric nonlocal coupling. These findings are verified by direct numerical integration of the full equations with nonlocal coupling.

  9. The role of noninnocent solvent molecules in organocatalyzed asymmetric Michael addition reactions.

    Science.gov (United States)

    Patil, Mahendra P; Sunoj, Raghavan B

    2008-01-01

    A proline-catalyzed asymmetric Michael addition between ketones and trans-beta-nitrostyrene was studied by using the density-functional theory with mPW1PW91 and B3LYP functionals. Improved insight into the enantio- and diastereoselective formation of gamma-nitroketones/-aldehydes is obtained through transition-state analysis. Consideration of the activation parameters obtained from gas-phase calculations and continuum solvation models failed to reproduce the reported experimental stereoselectivities for the reaction between cyclohexanone and 3-pentanone with trans-beta-nitrostyrene. The correct diastereo- and enantioselectivites were obtained only upon explicit inclusion of solvent molecules in the diastereomeric transition states that pertain to the C--C bond formation. Among the several transition-state models that were examined, the one that exhibits cooperative hydrogen-bonding interactions with two molecules of methanol could explain the correct stereochemical outcome of the Michael reaction. The change in differential stabilization that arises as a result of electrostatic and hydrogen-bonding interactions in the key transition states is identified as the contributing factor toward obtaining the correct diastereomer. This study establishes the importance of including explicit solvent molecules in situations in which the gas-phase and continuum models are inadequate in obtaining meaningful insight regarding experimental stereoselectivities.

  10. Synthesis of sulphonated mesoporous phenolic resins and their application in esterification and asymmetric aldol reactions

    Energy Technology Data Exchange (ETDEWEB)

    Muylaert, Ilke [Department of Inorganic and Physical Chemistry, Ghent University, Center for Ordered Materials, Organometallics and Catalysis (COMOC), Krijgslaan 281-S3, 9000 Ghent (Belgium); Verberckmoes, An, E-mail: an.verberckmoes@hogent.be [Department of Inorganic and Physical Chemistry, Ghent University, Center for Ordered Materials, Organometallics and Catalysis (COMOC), Krijgslaan 281-S3, 9000 Ghent (Belgium); Associated Faculty of Applied Engineering Sciences, University College Ghent, Valentin Vaerwyckweg 1, 9000 Ghent (Belgium); Spileers, Jeremy [Associated Faculty of Applied Engineering Sciences, University College Ghent, Valentin Vaerwyckweg 1, 9000 Ghent (Belgium); Demuynck, Anneleen; Peng, Li; De Clippel, Filip; Sels, Bert [Katholieke Universiteit Leuven, Centre for Surface Chemistry and Catalysis (COK), Kasteelpark Arenberg 23, 3001 Heverlee (Belgium); Van Der Voort, Pascal, E-mail: pascal.vandervoort@ugent.be [Department of Inorganic and Physical Chemistry, Ghent University, Center for Ordered Materials, Organometallics and Catalysis (COMOC), Krijgslaan 281-S3, 9000 Ghent (Belgium)

    2013-02-15

    Mesoporous phenolic resins were functionalized with sulphonic acid groups by four different types of sulphonation procedures: (i) direct sulphonation on the aromatic ring, (ii) alkyl sulphonation of the aromatic ring, and functionalizations of the phenolic hydroxyl surface by using an aryl silane, 2-(4-chlorosulphonylphenyl)ethyl trichlorosilane (iii) or a propyl silane, 3-mercaptopropyltrimethoxysilane (iv). The highest acidity loadings were obtained through direct sulphonation with fuming sulphuric acid (1.90 mmol H{sup +} g{sup −1}) or chlorosulphonic acid (1.31 mmol H{sup +} g{sup −1}) and these materials showed the highest conversion (97+ %) in Fischer esterification of acetic acid with propanol. However, the alkyl sulphonic groups, obtained through sulphonation procedure (ii) showed the highest stability in terms of maintenance of their acidity after use in consecutive catalytic runs or leaching treatments. This was demonstrated both through evaluation of the regenerated catalysts in a consecutive esterification run and during a leaching resistance test in aqueous medium. Moreover, the developed sulphonated mesoporous phenolic resins are presented as novel support for the non-covalent immobilization of an L-phenylalanine derived chiral diamine organocatalyst for asymmetric aldol reactions. The immobilization is established by an acid–base interaction between the sulphonic acid group and the amine function. The acidity and in particular the electronic withdrawing environment of the sulphonic acid groups influence enormously the catalytic performance of the non-covalent immobilized chiral diamine catalyst (aromatic > aliphatic). - Highlights: ► Different types of sulphonation procedures for mesoporous phenolic resins. ► Influence of acidity and electronic withdrawing environment. ► Novel support for non-covalent immobilization of chiral diamine catalyst. ► Catalytic performance in esterification and asymmetric aldol condensation. ► Demonstration

  11. Organocatalytic Asymmetric Synthesis of Functionalized 1,3,5-Triarylpyrrolidin-2-ones via an Aza-Michael/Aldol Domino Reaction.

    Science.gov (United States)

    Joie, Céline; Deckers, Kristina; Enders, Dieter

    2014-03-01

    The organocatalytic asymmetric synthesis of functionalized 1,3,5-triarylpyrrolidin-2-ones bearing three contiguous stereocenters through an aza-Michael/aldol domino reaction of α-ketoamides with α,β-unsaturated aldehydes is described. The domino products were further derivatized by aldehyde olefination under one-pot conditions. The reaction proceeds with excellent diastereoselectivities (>20:1) and good to excellent enantioselectivities (60-96% ee).

  12. Enantio- and diastereoselectivities in chiral sulfur ylide promoted asymmetric aziridination reactions.

    Science.gov (United States)

    Janardanan, Deepa; Sunoj, Raghavan B

    2008-11-07

    Density functional theory investigation on the factors controlling enantio- and diastereoselection in asymmetric aziridination reaction by the addition of chiral bicyclic sulfur ylides to substituted aldimines is presented. High levels of enantioselection are predicted toward the formation of (2S,3S)-cis and (2R,3S)-trans aziridines by the addition of stabilized ylide (R = COMe) respectively to SO2Me and CO2Me protected aldimines. Similarly, high %ee is predicted for the formation of (2S,3R)-cis aziridines from semistabilized (R = Ph) ylide. Moderate to high levels of diastereoselectivity is noticed as well. The present study highlights that a correct prediction on extent of enantioselection requires the knowledge of the activation barriers for elementary steps beyond the initial addition step. In the case of stabilized ylides the ring-closure (or elimination of sulfur compound) is found to be crucial in controlling enantio- and diastereoselection. A cumulative effect of electronic as well as other weak interactions is identified as factors contributing to the relative energies of transition states leading to enantio- and diastereomeric products for the stabilized ylide addition to aldimines. On the contrary, steric control appears quite dominant with semistabilized ylide addition. With the smallest substituent on ylide (R = Me), high enantioselectivity is predicted for the formation of (2R,3R)-trans aziridines although the %de in this case is found to be very low.

  13. New Chiral Pyridine Prolinol Derivatives and Preliminary Study on Asymmetric Catalytic Reaction

    Institute of Scientific and Technical Information of China (English)

    Xiao CHEN; Yong Xin ZHANG; Da Ming DU; Wen Ting HUA

    2004-01-01

    Two new chiral pyridine prolinol derivatives have been synthesized from N-alkylation of (S)-α,α-diphenyl-2-pyrrolidinemethanol with 2-bromomethylpyridine and 2, 6-dibromo-methyl-pyridine. The catalytic asymmetric borane reduction of prochiral ketones and the asymmetric addition of diethylzinc to benzaldehyde were investigated.

  14. Stereoselective Synthesis of trans-Olefins by the Copper-Mediated SN2′ Reaction of Vinyl Oxazines with Grignard Reagents. Asymmetric Synthesis of D-threo-Sphingosines

    OpenAIRE

    Singh, Om V; Han, Hyunsoo

    2007-01-01

    The SN2′ reaction of 6-vinyl-5,6-dihydro-4H-[1,3]oxazines with Grignard reagents in the presence of CuCN was studied, and high trans selectivity for the formation of double bond was observed with a variety of RMgX. The SN2′ reaction, coupled with regioselective asymmetric aminohydroxylation reaction, provided a highly efficient route for the asymmetric synthesis of D-threo-N-acetylsphingosine.

  15. Preparation of Poly(ionic liquid)s-Supported Recyclable Organocatalysts for the Asymmetric Nitroaldol (Henry) Reaction.

    Science.gov (United States)

    Großeheilmann, Julia; Bandomir, Jenny; Kragl, Udo

    2015-12-21

    A novel strategy for the embedding of quinine-based organocatalysts in polymerized ionic liquids-based hydrogels is presented. With this technique, the encapsulated organocatalyst was successfully recovered and reused for four cycles without any loss of enantioselectivity (up to 91% ee) for the asymmetric nitroaldol (Henry) reaction. In this study, high catalyst leaching was significantly reduced (water content. After catalyst removal, evaporation of the solvent affords the product in 98% purity without any further purification.

  16. Asymmetric recombination and electron spin relaxation in the semiclassical theory of radical pair reactions

    Energy Technology Data Exchange (ETDEWEB)

    Lewis, Alan M.; Manolopoulos, David E.; Hore, P. J. [Department of Chemistry, University of Oxford, Physical and Theoretical Chemistry Laboratory, South Parks Road, Oxford OX1 3QZ (United Kingdom)

    2014-07-28

    We describe how the semiclassical theory of radical pair recombination reactions recently introduced by two of us [D. E. Manolopoulos and P. J. Hore, J. Chem. Phys. 139, 124106 (2013)] can be generalised to allow for different singlet and triplet recombination rates. This is a non-trivial generalisation because when the recombination rates are different the recombination process is dynamically coupled to the coherent electron spin dynamics of the radical pair. Furthermore, because the recombination operator is a two-electron operator, it is no longer sufficient simply to consider the two electrons as classical vectors: one has to consider the complete set of 16 two-electron spin operators as independent classical variables. The resulting semiclassical theory is first validated by comparison with exact quantum mechanical results for a model radical pair containing 12 nuclear spins. It is then used to shed light on the spin dynamics of a carotenoid-porphyrin-fullerene triad containing considerably more nuclear spins which has recently been used to establish a “proof of principle” for the operation of a chemical compass [K. Maeda, K. B. Henbest, F. Cintolesi, I. Kuprov, C. T. Rodgers, P. A. Liddell, D. Gust, C. R. Timmel, and P. J. Hore, Nature (London) 453, 387 (2008)]. We find in particular that the intriguing biphasic behaviour that has been observed in the effect of an Earth-strength magnetic field on the time-dependent survival probability of the photo-excited C{sup ·+}PF{sup ·−} radical pair arises from a delicate balance between its asymmetric recombination and the relaxation of the electron spin in the carotenoid radical.

  17. Organocatalytic Domino Oxa-Michael/1,6-Addition Reactions: Asymmetric Synthesis of Chromans Bearing Oxindole Scaffolds.

    Science.gov (United States)

    Zhao, Kun; Zhi, Ying; Shu, Tao; Valkonen, Arto; Rissanen, Kari; Enders, Dieter

    2016-09-19

    An asymmetric organocatalytic domino oxa-Michael/1,6-addition reaction of ortho-hydroxyphenyl-substituted para-quinone methides and isatin-derived enoates has been developed. In the presence of 5 mol % of a bifunctional thiourea organocatalyst, this scalable domino reaction affords 4-phenyl-substituted chromans bearing spiro-connected oxindole scaffolds and three adjacent stereogenic centers in good to excellent yields (up to 98 %) and with very high stereoselectivities (up to >20:1 d.r., >99 % ee). © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Correction: A highly enantioselective Biginelli reaction using self-assembled methanoproline-thiourea organocatalysts: asymmetric synthesis of 6-isopropyl-3,4-dihydropyrimidines.

    Science.gov (United States)

    Hang, Zhijun; Zhu, Jun; Lian, Xiang; Xu, Peng; Yu, Han; Han, Sheng

    2016-02-07

    Correction for 'A highly enantioselective Biginelli reaction using self-assembled methanoproline-thiourea organocatalysts: asymmetric synthesis of 6-isopropyl-3,4-dihydropyrimidines' by Zhijun Hang et al., Chem. Commun., 2016, 52, 80-83.

  19. Proline Catalyzed Asymmetric Aldol Reaction between Methyl Ketones and 1-Aryl-2,2,2-trifluoroethanones

    Institute of Scientific and Technical Information of China (English)

    QIU Li-Hua; SHEN Zong-Xuan; SHI Chang-Qing; LIU Yan-Hua; ZHANG Ya-Wen

    2005-01-01

    Direct asymmetric aldol addition of methyl ketones to 2,2,2-trifluoro-1-phenylethanone and its ring-substituted derivatives was achieved using L-proline as a chiral promoter. Various optically active β-trifluoromethyl-β-hydroxy ketones were obtained in almost quantitative yields with moderate enantioselectivities up to 64 % ee.

  20. Rational Design and Synthesis of [5]Helicene-Derived Phosphine Ligands and Their Application in Pd-Catalyzed Asymmetric Reactions

    Science.gov (United States)

    Yamamoto, Kosuke; Shimizu, Takashi; Igawa, Kazunobu; Tomooka, Katsuhiko; Hirai, Go; Suemune, Hiroshi; Usui, Kazuteru

    2016-11-01

    A series of novel optically active [5]helicene-derived phosphine ligands (L1, with a 7,8-dihydro[5]helicene core structure- and L2, with a fully aromatic [5]helicene core structure) were synthesized. Despite their structural similarities, L1 and L2 exhibit particularly different characteristics in their use as chiral ligands. L1 was highly effective in the asymmetric allylation of indoles with 1,3-diphenylallyl acetate (up to 99% ee), and in the etherification of alcohols (up to 96% ee). In contrast, L2 was highly effective in the stereocontrol of helical chirality in Suzuki-Miyaura coupling (SMC) reaction (up to 99% ee). Density functional theory analysis was employed to propose a model that accounts for the origin of the enantioselectivity in these reactions.

  1. Asymmetric Michael Reaction of Malononitrile Catalyzed by Chiral Ru(Ⅱ) Complex and Achiral Base

    Institute of Scientific and Technical Information of China (English)

    MA Ya-Ping; XING Zhi-Kui; ZHU Jin; CUI Xin; CUN Lin-Feng; DENG Jin-Gen

    2003-01-01

    @@ Michael addition reactions represent one of the most important carbon-carbon bond forming reactions in modern synthetic organic chemistry. [1 ~3] We achieved catalytic enantioselective Michael addition reactions of malononitrile with chiral vicinal diamine-Ru(Ⅱ) complex in the presence of achiral base. High yields and moderate ee were observed.

  2. Refined transition-state models for proline-catalyzed asymmetric Michael reactions under basic and base-free conditions.

    Science.gov (United States)

    Sharma, Akhilesh K; Sunoj, Raghavan B

    2012-12-07

    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.

  3. Bifunctional nanocrystalline MgO for chiral epoxy ketones via Claisen-Schmidt condensation-asymmetric epoxidation reactions.

    Science.gov (United States)

    Choudary, Boyapati M; Kantam, Mannepalli L; Ranganath, Kalluri V S; Mahendar, Koosam; Sreedhar, Bojja

    2004-03-24

    Design and development of a truly nanobifunctional heterogeneous catalyst for the Claisen-Schmidt condensation (CSC) of benzaldehydes with acetophenones to yield chalcones quantitatively followed by asymmetric epoxidation (AE) to afford chiral epoxy ketones with moderate to good yields and impressive ee's is described. The nanomagnesium oxide (aerogel prepared) NAP-MgO was found to be superior over the NA-MgO and CM-MgO in terms of activity and enantioselectivity as applicable in these reactions. An elegant strategy for heterogenization of homogeneous catalysts is presented here to evolve single-site chiral catalysts for AE by a successful transfer of molecular chemistry to surface metal-organic chemistry with the retention of activity, selectivity/enantioselectivity. Brønsted hydroxyls are established as sole contributors for the epoxidation reaction, while they add on to the CSC, which is largely driven by Lewis basic O2-sites. Strong hydrogen-bond interactions between the surface -OH on MgO and -OH groups of diethyl tartrate are found inducing enantioselectivity in the AE reaction. Thus, the nanocrystalline NAP-MgO with its defined shape, size, and accessible OH groups allows the chemisorption of TBHP, DET, and olefin on its surface to accomplish single-site chiral catalysts to provide optimum ee's in AE reactions.

  4. Possibilities of synthesis of unknown isotopes of superheavy nuclei with charge numbers Z > 108 in asymmetric actinide-based complete fusion reactions

    Energy Technology Data Exchange (ETDEWEB)

    Hong, Juhee [Institute for Basic Science, Rare Isotope Science Project, Daejeon (Korea, Republic of); Adamian, G.G. [Joint Institute for Nuclear Research, Dubna (Russian Federation); Antonenko, N.V. [Joint Institute for Nuclear Research, Dubna (Russian Federation); Tomsk Polytechnic University, Mathematical Physics Department, Tomsk (Russian Federation)

    2016-10-15

    The possibilities of production of new isotopes of superheavy nuclei with charge numbers Z = 109-114 in various asymmetric hot fusion reactions are studied for the first time. The excitation functions of the formation of these isotopes in the xn evaporation channels are predicted and the optimal conditions for the synthesis are proposed. The products of the suggested reactions can fill a gap of unknown isotopes between the isotopes of the heaviest nuclei obtained in cold and hot complete fusion reactions. (orig.)

  5. Possibilities of synthesis of unknown isotopes of superheavy nuclei with charge numbers Z > 108 in asymmetric actinide-based complete fusion reactions

    Science.gov (United States)

    Hong, Juhee; Adamian, G. G.; Antonenko, N. V.

    2016-10-01

    The possibilities of production of new isotopes of superheavy nuclei with charge numbers Z = 109-114 in various asymmetric hot fusion reactions are studied for the first time. The excitation functions of the formation of these isotopes in the xn evaporation channels are predicted and the optimal conditions for the synthesis are proposed. The products of the suggested reactions can fill a gap of unknown isotopes between the isotopes of the heaviest nuclei obtained in cold and hot complete fusion reactions.

  6. A general approach to synthesize asymmetric hybrid nanoparticles by interfacial reactions.

    Science.gov (United States)

    He, Jie; Perez, Maria Teresa; Zhang, Peng; Liu, Yijing; Babu, Taarika; Gong, Jinlong; Nie, Zhihong

    2012-02-29

    Asymmetric multicomponent nanoparticles (AMNPs) offer new opportunities for new-generation materials with improved or new synergetic properties not found in their individual components. There is, however, an urgent need for a synthetic strategy capable of preparing hybrid AMNPs with fine-tuned structural and compositional complexities. Herein, we report a new paradigm for the controllable synthesis of polymer/metal AMNPs with well-controlled size, shape, composition, and morphology by utilizing interfacial polymerization. The hybrid AMNPs display a new level of structural-architectural sophistication, such as controlled domain size and the number of each component of AMNPs. The approach is simple, versatile, cost-effective, and scalable for synthesizing large quantities of AMNPs. Our method may pave a new route to the design and synthesis of advanced breeds of building blocks for functional materials and devices. © 2012 American Chemical Society

  7. Asymmetric Neutrino Reaction in Magnetized Proto-Neutron Stars in Fully Relativistic Approach

    Directory of Open Access Journals (Sweden)

    Yasutake Nobutoshi

    2012-02-01

    Full Text Available We calculate asymmetric neutrino absorption and scattering cross sections on hot and dense magnetized neutron-star matter including hyperons in fully relativistic mean-field theory. The absorption/scattering cross sections are suppressed/enhanced incoherently in the direction of the magnetic field B = Bẑ. The asymmetry is 2–4% at the matter density ρ0 ≤ ρB ≤ 3ρ0 and temperature T ≤ 40MeV for B = 2 × 1017G. Then we solve the Boltzmann equation for the neutrino transport in 1D attenuation approximation, and get the result that the kick velocity becomes about 300 km/s for the proto-neutron star with 168 solar mass at T = 20MeV.

  8. 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)

    2015-01-15

    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.

  9. Chirality imprinting and direct asymmetric reaction screening using a stereodynamic Brønsted/Lewis acid receptor

    Science.gov (United States)

    Bentley, Keith W.; Proano, Daysi; Wolf, Christian

    2016-08-01

    Molecular recognition, activation and dynamic self-assembly with Brønsted and Lewis acids play a central role across the chemical sciences including catalysis, crystal engineering, supramolecular architectures and drug design. Despite this general advance, the utilization of the corresponding binding motifs for fast and robust quantitative chemosensing of chiral compounds in a complicate matrix has remained challenging. Here we show that a stereodynamic probe carrying complementary boronic acid and urea units achieves this goal with hydroxy carboxylic acids. Synergistic dual-site binding and instantaneous chirality imprinting result in characteristic ultraviolet and CD readouts that allow instantaneous determination of the absolute configuration, enantiomeric excess and concentration of the target compound even in complex mixtures. The robustness and practicality of this strategy for high-throughput screening purposes is demonstrated. Comprehensive sensing of only 0.5 mg of a crude reaction mixture of an asymmetric reduction eliminates cumbersome work-up protocols and minimizes analysis time, labour and waste production.

  10. Versatile In Situ Generated N-Boc-Imines: Application to Phase-Transfer-Catalyzed Asymmetric Mannich-Type Reactions.

    Science.gov (United States)

    Kano, Taichi; Kobayashi, Ryohei; Maruoka, Keiji

    2015-07-13

    The efficient construction of nitrogen-containing organic compounds is a major challenge in chemical synthesis. Imines are one of the most important classes of electrophiles for this transformation. However, both the available imines and applicable nucleophiles for them are quite limited given the existing preparative methods. Described herein are imine precursors which generate reactive imines with a wide variety of substituents under mild basic conditions. This approach enables the construction of various nitrogen-containing molecules which cannot be accessed by the traditional approach. The utility of the novel imine precursor was demonstrated in the asymmetric Mannich-type reaction under phase-transfer conditions. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Lithium amide assisted asymmetric Mannich-type reactions of menthyl acetate with PMP-aldimines.

    Science.gov (United States)

    Hata, Seiji; Iguchi, Mayu; Iwasawa, Tetsuo; Yamada, Ken-ichi; Tomioka, Kiyoshi

    2004-05-27

    A lithium enolate of menthyl acetate added to PMP-imines, in the presence of an equimolar amount of lithium diisopropylamide, affords the Mannich-type addition products in high stereoselectivity. [reaction--see text

  12. Asymmetric Synthesis of Functionalized Tricyclic Chromanes via an Organocatalytic Triple Domino Reaction.

    Science.gov (United States)

    Kumar, Mukesh; Chauhan, Pankaj; Valkonen, Arto; Rissanen, Kari; Enders, Dieter

    2017-06-02

    A highly stereoselective triple domino reaction for the synthesis of functionalized tricyclic chromane scaffolds has been developed. A secondary amine-catalyzed domino Michael/Michael/aldol condensation reaction between aliphatic aldehydes, nitro-chromenes, and α,β-unsaturated aldehydes leads to the formation of synthetically important tricyclic chromanes bearing four contiguous stereogenic centers including a tetrasubstituted carbon in good yields (20-66%) and excellent stereoselectivities (>20:1 dr and >99% ee).

  13. Asymmetric Glyoxylate-Ene Reactions Catalyzed by Chiral Pd(II Complexes in the Ionic Liquid [bmim][PF6

    Directory of Open Access Journals (Sweden)

    Nan Sun

    2007-06-01

    Full Text Available The room temperature ionic liquid [bmim][PF6] was employed as the reactionmedium in the asymmetric glyoxylate-ene reaction of α-methyl styrene (4a with ethylglyoxylate using chiral palladium(II complexes as the catalysts. [Pd(S-BINAP(3,5-CF3-PhCN2](SbF62 (1b showed the highest catalytic activity. Under the reaction conditionsof 40 oC, 0.5 h, and 1b/4a molar ratio of 0.05, ethyl α-hydroxy-4-phenyl-4-pentenoate wasobtained in excellent chemical yield (94 % with high enantioselectivity (70 %. Otherα-hydroxy esters can also be obtained in high chemical yields and enantioselectitiesthrough the glyoxylate-ene reactions of alkenes with glyoxylates catalyzed by 1b in[bmim][PF6]. Moreover, the ionic liquid [bmim][PF6] which contained the palladium(IIcomplex could be recycled and reused several times without significant loss of the catalyticactivity.

  14. Brønsted-acid-catalyzed asymmetric multicomponent reactions for the facile synthesis of highly enantioenriched structurally diverse nitrogenous heterocycles.

    Science.gov (United States)

    Yu, Jie; Shi, Feng; Gong, Liu-Zhu

    2011-11-15

    Optically pure nitrogenous compounds, and especially nitrogen-containing heterocycles, have drawn intense research attention because of their frequent isolation as natural products. These compounds have wide-ranging biological and pharmaceutical activities, offering potential as new drug candidates. Among the various synthetic approaches to nitrogenous heterocycles, the use of asymmetric multicomponent reactions (MCRs) catalyzed by chiral phosphoric acids has recently emerged as a particularly robust tool. This method combines the prominent merits of MCRs with organocatalysis, thus affording enantio-enriched nitrogenous heterocyclic compounds with excellent enantioselectivity, atom economy, bond-forming efficiency, structural diversity, and complexity. In this Account, we discuss a variety of asymmetric MCRs catalyzed by chiral phosphoric acids that lead to the production of structurally diverse nitrogenous heterocycles. In MCRs, three or more reagents are combined simultaneously to produce a single product containing structural contributions from all the components. These one-pot processes are especially useful in the construction of heterocyclic cores: they can provide a high degree of both complexity and diversity for a targeted set of scaffolds while minimizing the number of synthetic operations. Unfortunately, enantioselective MCRs have thus far been relatively underdeveloped. Particularly lacking are reactions that proceed through imine intermediates, which are formed from the condensation of carbonyls and amines. The concomitant generation of water in the condensation reaction can deactivate some Lewis acid catalysts, resulting in premature termination of the reaction. Thus, chiral catalysts typically must be compatible with water for MCRs to generate nitrogenous compounds. Recently, organocatalytic MCRs have proven valuable in this respect. Brønsted acids, an important class of organocatalysts, are highly compatible with water and thereby offer great

  15. Crystallization and solid-state reaction as a route to asymmetric synthesis from achiral starting materials.

    Science.gov (United States)

    Green, B S; Lahav, M

    1975-10-29

    Many molecules which are achiral can crystallize in chiral (enantiomorphic) crystals and, under suitable conditions, crystals of only one chirality may be obtained. The formation of right- or left-handed crystals in excess is equally probable. Lattice-controlled (topochemical) photochemical or thermal solid-state reactions may then afford stable, optically active products. In the presence of the chiral products, achiral reactants may preferentially produce crystals of one chirality, leading to a feedback mechanism for the generation and amplification of optical activity. Amplification of optical activity can also be achieved by solid-state reactions. The optical synthesis of biologically relevant compounds by such routes may be envisaged.

  16. Analysis of the role of neutron transfer in asymmetric fusion reactions at subbarrier energies

    Energy Technology Data Exchange (ETDEWEB)

    Ogloblin, A. A. [National Research Center Kurchatov Institute (Russian Federation); Zhang, H. Q.; Lin, C. J.; Jia, H. M. [China Institute of Atomic Energy (China); Khlebnikov, S. V. [Khlopin Radium Institute (Russian Federation); Kuzmin, E. A.; Danilov, A. N.; Demyanova, A. S. [National Research Center Kurchatov Institute (Russian Federation); Trzaska, W. H. [University of Jyväskylä, Department of Physics (Finland); Xu, X. X. [China Institute of Atomic Energy (China); Yang, F. [National Research Center Kurchatov Institute (Russian Federation); Sargsyan, V. V., E-mail: sargsyan@theor.jinr.ru; Adamian, G. G.; Antonenko, N. V. [Joint Institute for Nuclear Research (Russian Federation); Scheid, W. [Institüt für Theoretische Physik der Justus-Liebig-Universität (Germany)

    2015-12-15

    The excitation functions were measured for the {sup 28}Si + {sup 208}Pb complete-fusion (capture) reaction at deep subbarrier energies. The results were compared with the cross sections predicted within the quantum diffusion approach. The role of neutron transfer in the case of positive Q values in the {sup 28}Si + {sup 124}Sn, {sup 208}Pb; {sup 30}Si + {sup 124}Sn, {sup 208}Pb; {sup 20}Ne + {sup 208}Pb; {sup 40}Ca + {sup 96}Zr; and {sup 134}Te + {sup 40}Ca complete-fusion (capture) reactions is discussed.

  17. Pybox monolithic miniflow reactors for continuous asymmetric cyclopropanation reaction under conventional and supercritical conditions.

    Science.gov (United States)

    Burguete, M I; Cornejo, A; García-Verdugo, E; Gil, María J; Luis, S V; Mayoral, J A; Martínez-Merino, V; Sokolova, M

    2007-06-08

    Supported catalysts having pybox chiral moieties were prepared as macroporous monolithic miniflow systems. These catalysts are based on styrene-divinylbenzene polymeric backbones having different compositions and pybox chiral moieties. Their corresponding ruthenium complexes were tested for the continuous flow cyclopropanation reaction between styrene and ethyldiazoacetate (EDA) under conventional conditions and in supercritical carbon dioxide (scCO2). Ru-Pybox monolithic miniflow reactors not only provided a highly efficient and robust heterogeneous chiral catalyst but also allowed us to develop more environmental reaction conditions without sacrificing the global efficiency of the process.

  18. 1-Azadienes as regio- and chemoselective dienophiles in aminocatalytic asymmetric Diels-Alder reaction.

    Science.gov (United States)

    Ma, Chao; Gu, Jing; Teng, Bin; Zhou, Qing-Qing; Li, Rui; Chen, Ying-Chun

    2013-12-20

    Electron-deficient 1-aza-1,3-butadienes containing a 1,2-benzoisothiazole-1,1-dioxide or 1,2,3-benzoxathiazine-2,2-dioxide motif act as regio- and chemoselective dienophiles in normal-electron-demand Diels-Alder reactions with HOMO-raised trienamines, rather than typical 4π-participation in inverse-electron-demand versions. The enantioenriched cycloadducts could be efficiently converted to spiro or fused frameworks with high structural and stereogenic complexity by a sequential aza-benzoin reaction or other transformations.

  19. Asymmetric and efficient synthesis of homophenylalanine derivatives via Friedel-Crafts reaction with trifluoromethanesulfonic acid

    OpenAIRE

    Murashige, Ryo; Hayashi, Yuka; Hashimoto, Makoto; 橋本, 誠

    2008-01-01

    An efficient Friedel-Crafts reaction of TFA-Asp(Cl)-OMe and stoichiometric amounts of benzene was established by using neat trifluoromethanesulfonic acid (TfOH) as solvent and catalyst under a mild condition. This methodology has been applied to many aromatic compounds and enabled synthesis of several homophenylalanine derivatives.

  20. Chiral ammonium betaine-catalyzed asymmetric Mannich-type reaction of oxindoles

    Directory of Open Access Journals (Sweden)

    Masahiro Torii

    2016-09-01

    Full Text Available A highly diastereo- and enantioselective Mannich-type reaction of 3-aryloxindoles with N-Boc aldimines was achieved under the catalysis of axially chiral ammonium betaines. This catalytic method provides a new tool for the construction of consecutive quaternary and tertiary stereogenic carbon centers on biologically intriguing molecular frameworks with high fidelity.

  1. Solvent Effects in Asymmetric Hetero Diels-Alder and Ene Reactions

    DEFF Research Database (Denmark)

    Johannsen, Mogens; Jørgensen, Karl Anker

    1996-01-01

    The use of polar solvents such as nitromethane or 2-nitropropane leads to a significant improvement of the catalytic properties of a cationic copper-Lewis acid in the hetero Diels-Alder reaction of alkyl glyoxylates with dienes; The scope of a newly developed copper(II)-bisoxazoline catalyst...

  2. Asymmetric Baylis-Hillman Reaction between Chiral Activated Alkenes and Aromatic Aldehydes in Me3N/H2O/Solvent Medium

    Institute of Scientific and Technical Information of China (English)

    Ke HE; Zheng Hong ZHOU; Hong Ying TANG; Guo Feng ZHAO; Chu Chi TANG

    2005-01-01

    Chiral activated alkene, L-menthyl acrylate and (+)-N-α-phenylethyl acrylamide,induced asymmetric Baylis-Hillman reaction of aromatic aldehydes was realized at 25℃ for 7 days in Me3N/H2O/solvent homogeneous medium. The corresponding Baylis-Hillman adducts were obtained in good chemical yield with moderate to excellent diastereoselectivity (up to 99% de).

  3. Mechanism and electronic effects in nitrogen ylide-promoted asymmetric aziridination reaction.

    Science.gov (United States)

    Rajeev, Ramanan; Sunoj, Raghavan B

    2011-04-07

    The mechanism and stereoselectivity of the aziridination reaction between guanidinium ylide and a series of para-substituted benzaldehydes have been studied by using density functional theory methods. The mechanistic details and analyses of the key elementary steps involved in (a) the addition of nitrogen ylide to benzaldehydes and (b) subsequent fragmentation of the resulting oxaspirocyclic intermediate are presented. The relative energies of important transition states and intermediates are found to be useful toward rationalizing reported diastereoselective product formation. The relative energies of the key transition states could be rationalized on the basis of the differences in steric, electrostatic, and other stabilizing weak interactions. The deformation analysis of the transition state geometries exhibited good correlation with the predicted activation barriers. The changes in cis/trans diastereoselectivity preferences upon changes in the electron donating/withdrawing abilities of the para substituents on benzaldehyde are identified as arising due to vital differences in the preferred pathways. The large value of reaction constant (ρ > 4.8) estimated from the slope of good linear Hammett plots indicated high sensitivity to the electronic nature of substituents on benzaldehyde. The formation of trans-aziridine in the case of strong electron donating groups and cis-aziridines with weakly electron donating/withdrawing group has been explained by the likely changes in the mechanistic course of the reaction. In general, the predicted trends are found to be in good agreement with the earlier experimental reports.

  4. N-heterocyclic carbene catalyzed asymmetric intermolecular Stetter reaction: origin of enantioselectivity and role of counterions.

    Science.gov (United States)

    Kuniyil, Rositha; Sunoj, Raghavan B

    2013-10-04

    The mechanism and the role of KOtBu in an enantioselective NHC-catalyzed Stetter reaction between p-chlorobenzaldehyde and N-acylamido acrylate is established using DFT(M06-2X) methods. The Gibbs free energies are found to be significantly lower for transition states with explicit bound KOtBu as compared to the conventional pathways without the counterions. An intermolecular proton transfer from HOtBu to the prochiral carbon is identified as the stereocontrolling step. The computed enantioselectivities are in excellent agreement with the experimental results.

  5. Noninnocent role of N-methyl pyrrolidinone in thiazolidinethione-promoted asymmetric aldol reactions.

    Science.gov (United States)

    Sreenithya, A; Sunoj, Raghavan B

    2012-11-16

    The origin of stereoselectivity in the reaction between α-azido titanium enolate derived from chiral auxiliary N-acyl thiazolidinethione and benzaldehyde is established using the DFT(B3LYP) method. A nonchelated transition state with N-methyl-2-pyrrolidinone (NMP) bound to a TiCl(3) enolate is found to be energetically the most preferred model responsible for the formation of an Evans syn aldol product. The TS model devoid of NMP, although of higher energy, is found to be successful in predicting the right stereochemical outcome.

  6. Asymmetric carbon-carbon bond forming reactions catalyzed by chiral titanium complexes. Efficient synthesis of optically active secondary alcohols; Kiraru na chitan shokubai ni yoru fuseitanso-tanso ketsugo keisei. Kogaku kassei dainikyu arukoru no gosei

    Energy Technology Data Exchange (ETDEWEB)

    Hayashi, M. [Yamaguchi Univ., Yamaguchi (Japan). Faculty of Science

    1996-02-01

    For asymmetric metal complex catalysts with high catalytic activity and ability for recognizing asymmetry, it is most important to choose center metals and design asymmetric organic ligands. When the authors began to study on the title reactions, combination of titanium alkoxides as center metals and chiral Schiff bases as organic ligands was unknown, although two moieties had been used independently for asymmetric reactions with excellent results. Asymmetric silylcyanation of aldehydes and enantio-selective addition of diketone to aldehydes are introduced, that have been achieved by authors using titanium complexes of the above combination. In the silylcyanation, reactivity is remarkably improved, compared with a single catalyst of titanium isopropoxide. Cyanohydrin of R from was obtained preferentially with salicyladehyde, particularly having 3-tert butyl group, in an asymmetric yield of 85 % ee. In the latter addition reaction, 5-hydroxy-3-ketoesters were obtained from benzaldehyde in an asymmetric yield as high as 91 % ee. 9 refs., 2 figs.

  7. Asymmetric effect of mechanical stress on the forward and reverse reaction catalyzed by an enzyme.

    Directory of Open Access Journals (Sweden)

    Collin Joseph

    Full Text Available The concept of modulating enzymatic activity by exerting a mechanical stress on the enzyme has been established in previous work. Mechanical perturbation is also a tool for probing conformational motion accompanying the enzymatic cycle. Here we report measurements of the forward and reverse kinetics of the enzyme Guanylate Kinase from yeast (Saccharomyces cerevisiae. The enzyme is held in a state of stress using the DNA spring method. The observation that mechanical stress has different effects on the forward and reverse reaction kinetics suggests that forward and reverse reactions follow different paths, on average, in the enzyme's conformational space. Comparing the kinetics of the stressed and unstressed enzyme we also show that the maximum speed of the enzyme is comparable to the predictions of the relaxation model of enzyme action, where we use the independently determined dissipation coefficient [Formula: see text] for the enzyme's conformational motion. The present experiments provide a mean to explore enzyme kinetics beyond the static energy landscape picture of transition state theory.

  8. Dynamical Dipole and Equation of State in N/Z Asymmetric Fusion Reactions

    Directory of Open Access Journals (Sweden)

    Giaz Agnese

    2014-03-01

    Full Text Available In heavy ion reactions, in the case of N/Z asymmetry between projectile and target, the process leading to complete fusion is expected to produce pre-equilibrium dipole γ-ray emission. It is generated during the charge equilibration process and it is known as Dynamical Dipole. A new measurement of the dynamical dipole emission was performed by studying 16O + 116Sn at 12 MeV/u. These data, together with those measured at 8.1 MeV/u and 15.6 MeV/u for the same reaction, provide the dependence on the Dynamical Dipole total emission yield with beam energy and they can be compared with theoretical expectations. The experimental results show a weak increase of the Dynamical Dipole total yield with beam energies and are in agreement with the prediction of a theoretical model based on the Boltzmann–Nordheim–Vlasov (BNV approach. The measured trend with beam energy does not confirm the rise and fall behavior previously reported for the same fused compound but with a much higher dipole moment.

  9. Theoretical calculation of the triple differential cross sections of the 2p orbital of argon in a coplanar highly asymmetric (e, 2e) reaction

    Institute of Scientific and Technical Information of China (English)

    葛自明; 周雅君; 吕志伟; 王治文

    2002-01-01

    The triple differential cross sections of the 2p electron of argon in a coplanar highly asymmetric geometry have beencalculated with the modified distorted wave Born approximation (DWBA) and the target Hartree-Fock approximationmethods. The damping polarization of the semi-classical short-range potentials and the Mee factor are included in thedistorting potentials of the modified DWBA. Theoretical results are compared with a recent experiment. The dynamicmechanism of inner shell ionization in a coplanar highly asymmetric geometry (e, 2e) reaction are also discussed.

  10. Synthesis and evaluation of C-glycosides as hydrotropes and solubilizing agents

    Institute of Scientific and Technical Information of China (English)

    RANOUX; Adeline; LEMIEGRE; Loc; BENVEGNU; Thierry

    2010-01-01

    This work presents expeditious synthesis of C-glycoside amphiphiles in aqueous media from unprotected di-or mono-saccharides.A Horner-Wadsworth-Emmons/Michael addition/Barbier allylation sequence led to C-glycosides that exhibit hydrotropic properties.The hydrotropic and solubilizing properties of these homoallylic alcohols including a β-C-glycoside moiety as well as additional β-C-glycosidic ketones with a short(C7) alkyl chain are also described and compared with those of commercial O-glucoside references.

  11. Asymmetric recombination and electron spin relaxation in the semiclassical theory of radical pair reactions

    CERN Document Server

    Lewis, Alan M; Hore, P J

    2014-01-01

    We describe how the semiclassical theory of radical pair recombination reactions recently introduced by two of us [D. E. Manolopoulos and P. J. Hore, J. Chem. Phys. 139, 124106 (2013)] can be generalised to allow for different singlet and triplet recombination rates. This is a non-trivial generalisation because when the recombination rates are different the recombination process is dynamically coupled to the coherent electron spin dynamics of the radical pair. Furthermore, because the recombination operator is a two-electron operator, it is no longer sufficient simply to consider the two electrons as classical vectors: one has to consider the complete set of 16 two-electron spin operators as independent classical variables. The resulting semiclassical theory is first validated by comparison with exact quantum mechanical results for a model radical pair containing 12 nuclear spins. It is then used to shed light on the spin dynamics of a carotenoid-porphyrin-fullerene (CPF) triad containing considerably more nu...

  12. The asymmetric reactions of mean and volatility of stock returns to domestic and international information based on a four-regime double-threshold GARCH model

    Science.gov (United States)

    Chen, Cathy W. S.; Yang, Ming Jing; Gerlach, Richard; Jim Lo, H.

    2006-07-01

    In this paper, we investigate the asymmetric reactions of mean and volatility of stock returns in five major markets to their own local news and the US information via linear and nonlinear models. We introduce a four-regime Double-Threshold GARCH (DTGARCH) model, which allows asymmetry in both the conditional mean and variance equations simultaneously by employing two threshold variables, to analyze the stock markets’ reactions to different types of information (good/bad news) generated from the domestic markets and the US stock market. By applying the four-regime DTGARCH model, this study finds that the interaction between the information of domestic and US stock markets leads to the asymmetric reactions of stock returns and their variability. In addition, this research also finds that the positive autocorrelation reported in the previous studies of financial markets may in fact be mis-specified, and actually due to the local market's positive response to the US stock market.

  13. Asymmetric Fission in the 78Kr+40Ca reactions at 5.5 MeV/nucleon

    Directory of Open Access Journals (Sweden)

    Roy R.

    2012-02-01

    Full Text Available The cross section, kinetic energy distribution and angular distribution of fragments with atomic number 3 ≤ Z ≤ 28 emitted in the reaction 78Kr + 40Ca at the bombarding energy of 5.5 MeV/nucleon and coincidence between light charged particles and fragments were measured by means of the 4π-INDRA array to study the decay mechanism of medium mass excited nucleus. Global features indicate a high degree of relaxation and are compatible with a binary fission from compound nucleus. The mean value of the kinetic energy distributions of fragments indicates dominance of Coulomb interaction, while the width of the distribution signals large fluctuations. Inclusive cross-section distributions of fragments with charge 3 ≤ Z ≤ 28 are bell-shaped and a strong even-odd-staggering (o-es is observed for 3 ≤ Z ≤ 12. Coincidence measurements suggest that the light partners in very asymmetric fission are emitted at excitation energies below the particle emission thresholds. Data were confronted to the predictions of statistical model describing the decay of compound nuclei by emission of light particles and fragments. Calculations assuming spherical fission fragments and finite-range liquid drop fission barriers are not able to explain the experimental features. Attempts have been made to improve the agreement with experimental data. The analysis indicates the strong influence of the shape parameterization of the potential energy surface in describing the fission process of intermediate mass compound nuclei.

  14. Relative Stability of the Key Enamine,Oxazolidinone, and Imine Intermediates in Some Proline-catalyzed Asymmetric Reactions

    Institute of Scientific and Technical Information of China (English)

    HU Yi-Fan; LU Xin

    2008-01-01

    Many proline-catalyzed asymmetric addition reactions with ketones as substrates were assumed to involve a key intermediate, an enamine, produced by the condensation of proline and ketone. In this paper, the key intermediate enamines derived from L-proline and cyclohexanone (or acetone) as well as the corresponding oxazolidinone and imine tautomers have been investigated by means of density functional calculations at the B3LYP/6-311+G** level. The predicted order of stability for these tautomers is oxazolidinones > enamines > imines in gas phase and oxazolidinones > imines > enamines in aprotic THF solvent. This prediction explains why enamine intermediate can not be observed experimentally. The predicted energy/enthalpy difference between the formal oxazolidinone structure and the zwitterionic imine structures is very small in THF solvent, suggesting the oxazolidinone-to-imine tautomerization can be readily induced in solvent. 13C NMR chemical shifts of the oxazolidinone and imine structures have been computed and used to explain the experimental NMR spectra observed in oxazolidinone-to-imine tautomerization induced by protic solvent.

  15. A New Approach to the Asymmetric Reaction of the Chiron 5-L-Menthyloxy-2(5H)-furanones with Horner-Emmons Reagent

    Institute of Scientific and Technical Information of China (English)

    李学强; 王凤荣; 何兰; 陈庆华

    2003-01-01

    The asymmetric reaction of the chiron 2(5H )-furanones (4a-4c) with the Horner-Emmons reagents (5a-5b) has been investigated. The newly chirai organophosphorus derivatives 6 and 7 were obtained using the phosphoryl-stabilized carbanion as a building block in DMSO under mild conditions. Through the asymmetric introduction, the Horner-Emmons reagent could be transformed to a chiral building block to afford the novel functionalized phosphorus derivatives. The structures of the synthesized compounds 6 and 7 were identified on the basis of their elementary and spectroscopic data, such as IR,1H NMR, 13C NMR, MS and X-ray crystallography. These resuits provided a valuable approach to the synthesis of potentially interesting chirai organophosphorus derivatives and probing their biological activities.

  16. Additive Effects on Asymmetric Catalysis.

    Science.gov (United States)

    Hong, Liang; Sun, Wangsheng; Yang, Dongxu; Li, Guofeng; Wang, Rui

    2016-03-23

    This review highlights a number of additives that can be used to make asymmetric reactions perfect. Without changing other reaction conditions, simply adding additives can lead to improved asymmetric catalysis, such as reduced reaction time, improved yield, or/and increased selectivity.

  17. Diastereoselective Diels–Alder Reactions of N-Sulfonyl-1-aza-1,3-butadienes With Optically Active Enol Ethers: An Asymmetric Variant of the 1-Azadiene Diels–Alder Reaction

    Science.gov (United States)

    Clark, Ryan C.; Pfeiffer, Steven S.

    2008-01-01

    The first detailed study of a room temperature asymmetric Diels–Alder reaction of N-sulfonyl-1-aza-1,3-butadienes enlisting a series of nineteen enol ethers bearing chiral auxilaries is reported with many providing highly diastereoselective (endo and facial diastereoselection) reactions largely the result of an exquisitely organized [4 + 2] cycloaddition transition state. Three new, readily accessible, and previously unexplored auxilaries (18a, 19a and 37a) rationally emerged from the studies and provide remarkable selectivities (for 19a and 37a: 49:1 endo:exo and 48:1 facial selectivity) that promise to be useful in systems beyond those detailed. PMID:16492042

  18. An Environmentally Benign System for Synthesis of β-Hydroxylketones: L-Histidine Asymmetrically Catalyzed Direct Aldol Reactions in Aqueous Micelle and Water-like Media

    Institute of Scientific and Technical Information of China (English)

    PENG Yi-Yuan; PENG Shu-Jun; DING Qiu-Ping; WANG Qi; CHENG Jin-Pei

    2007-01-01

    The first histidine catalyzed direct aldol reactions of ketones with nitrobenzaldehydes in water and in poly(ethylene glycol) (PEG) were reported. It reveals that histidine is a good aldol catalyst for synthesis of β-hydroxylketones in water and in PEG, giving good to excellent yields of the respective products. Better enantioand regioselectivity were achieved using low molecular weight PEG as the media. The results show that histidine and PEG-200 or -300 may constitute a promising environmentally benign system for asymmetric synthesis of β-hydroxylketones.

  19. On Combined Effects of Heat Transfer and Chemical Reaction for the Flow through an Asymmetric Channel with Orthogonally Deformable Porous Walls

    Directory of Open Access Journals (Sweden)

    Syed Tauseef Mohyud-Din

    2016-01-01

    Full Text Available The combined effects of heat transfer and chemical reaction are studied for the flow through a semi-infinite asymmetric channel with orthogonally deformable porous walls. The similarity transforms have been used to reduce the conservation laws to a corresponding system of nonlinear ordinary differential equations. The resulting equations are solved, both analytically and numerically, by using Homotopy Analysis Method (HAM and the fourth-order Runge-Kutta (RK-4 method, respectively. The convergence of the analytical solution is assured through the so-called total squared residual error analysis. The optimal values of auxiliary parameters are obtained by minimizing the total squared residual error.

  20. Asymmetric Synthesis of Spirobenzazepinones with Atroposelectivity and Spiro-1,2-Diazepinones by NHC-Catalyzed [3+4] Annulation Reactions.

    Science.gov (United States)

    Wang, Lei; Li, Sun; Blümel, Marcus; Philipps, Arne R; Wang, Ai; Puttreddy, Rakesh; Rissanen, Kari; Enders, Dieter

    2016-09-05

    A strategy for the NHC-catalyzed asymmetric synthesis of spirobenzazepinones, spiro-1,2-diazepinones, and spiro-1,2-oxazepinones has been developed via [3+4]-cycloaddition reactions of isatin-derived enals (3C component) with in-situ-generated aza-o-quinone methides, azoalkenes, and nitrosoalkenes (4atom components). The [3+4] annulation strategy leads to the seven-membered target spiro heterocycles bearing an oxindole moiety in high yields and excellent enantioselectivities with a wide variety of substrates. Notably, the benzazepinone synthesis is atroposelective and an all-carbon spiro stereocenter is generated.

  1. Synthesis of New Chiral Benzimidazolylidene–Rh Complexes and Their Application in Asymmetric Addition Reactions of Organoboronic Acids to Aldehydes

    Directory of Open Access Journals (Sweden)

    Weiping He

    2016-09-01

    Full Text Available A series of novel chiral N-heterocyclic carbene rhodium complexes (NHC–Rh based on benzimidazole have been prepared, and all of the NHC–Rh complexes were fully characterized by NMR and mass spectrometry. These complexes could be used as catalysts for the asymmetric 1,2-addition of organoboronic acids to aldehydes, affording chiral diarylmethanols with high yields and moderate enantioselectivities.

  2. Polystyrene-supported cu(II)-R-Box as recyclable catalyst in asymmetric Friedel–Crafts reaction

    KAUST Repository

    Desyatkin, V. G.

    2017-02-12

    The complex of copper(II) trifluoromethanesulfonate with chiral isopropyl bis(oxazoline) ligand (i-Pr-Box) was immobilized on accessible and inexpensive Merrifield resin according to a “click” procedure. The resulting catalyst showed high efficiency and recyclability in the asymmetric Friedel–Crafts alkylation of indole and its derivatives. The catalyst can be recycled five times without appreciable loss in activity and enantioselectivity.

  3. A new synthesis of enantiomerically pure syn-(S)-β-hydroxy-α-amino acids via asymmetric aldol reactions of aldehydes with a homochiral Ni(II)-glycine/(S)-BPB Schiff base complex

    NARCIS (Netherlands)

    Belokon, Yuri N.; Kochetkov, Konstantin A.; Ikonnikov, Nikolai S.; Strelkova, Tatiana V.; Harutyunyan, Syuzanna R.; Saghiyan, Ashot S.

    2001-01-01

    syn-(S)-β-Hydroxy-α-amino acids were synthesised stereoselectively via elaboration of the asymmetric aldol reactions of aldehydes with a chiral Ni(II)-(S)-BPB/glycine Schiff base complex in the presence of equimolar NaH in THF. The stereoselectivity of the reaction was studied as a function of time,

  4. Application of Aromatic Nitroso Compounds in Asymmetric Reactions%芳香性亚硝基化合物在不对称反应中的应用(下)

    Institute of Scientific and Technical Information of China (English)

    王剑峰; 章迟啸; 刘雪粉

    2012-01-01

    综述了近年来芳香性亚硝基化合物在α-氨氧化、α-羟胺化和Diels-Alder等不对称反应中的研究进展。%The recently application of aromatic nitroso compounds as active agents in asymmetric reactions (such as α-aminoxylation reaction, α-oxyamination reaction and the Diels-Alder reaction)was reviewed.

  5. Asymmetric synthesis of α-amino-1,3-dithianes via chiral N-phosphonyl imine-based Umpolung reaction without using chromatography and recrystallization.

    Science.gov (United States)

    Kattamuri, Padmanabha V; Ai, Teng; Pindi, Suresh; Sun, Yinwei; Gu, Peng; Shi, Min; Li, Guigen

    2011-04-15

    A series of α-amino-1,3-dithianes have been synthesized via the asymmetric Umpolung reaction of 2-lithio-1,3-dithianes with chiral N-phosphonyl imines in good chemical yields (up to 82%) and good to excellent diastereoselectivities (>99:1). The manner by which chiral N-phosphonyl imines are slowly added into the solution of 2-lithio-1,3-dithiane was found to be crucial for achieving excellent diastereoselectivity. The current synthesis was proven to follow the GAP chemistry (group-assistant-purification chemistry) process, which avoids traditional purification techniques of chromatography or recrystallization, i.e., the pure chiral α-amino-1,3-dithianes attached with the chiral N-phosphonyl group were readily obtained by washing the solid crude products with hexane or a mixture of hexane-ethyl acetate.

  6. A-T linker adapter polymerase chain reaction for determining flanking sequences by rescuing inverse PCR or thermal asymmetric interlaced PCR products.

    Science.gov (United States)

    Trinh, Quoclinh; Zhu, Pengyu; Shi, Hui; Xu, Wentao; Hao, Junran; Luo, Yunbo; Huang, Kunlun

    2014-12-01

    The polymerase chain reaction (PCR)-based genome walking method has been extensively used to isolate unknown flanking sequences, whereas nonspecific products are always inevitable. To resolve these problems, we developed a new strategy to isolate the unknown flanking sequences by combining A-T linker adapter PCR with inverse PCR (I-PCR) or thermal asymmetric interlaced PCR (TAIL-PCR). The result showed that this method can be efficiently achieved with the flanking sequence from the Arabidopsis mutant and papain gene. Our study provides researchers with an additional method for determining genomic DNA flanking sequences to identify the target band from bulk of bands and to eliminate the cloning step for sequencing.

  7. Asymmetric synthesis of α-amino acids via homologation of Ni(II) complexes of glycine Schiff bases. Part 3: Michael addition reactions and miscellaneous transformations.

    Science.gov (United States)

    Aceña, José Luis; Sorochinsky, Alexander E; Soloshonok, Vadim

    2014-09-01

    The major goal of this review is a critical discussion of the literature data on asymmetric synthesis of α-amino acids via Michael addition reactions involving Ni(II)-complexes of amino acids. The material covered is divided into two conceptually different groups dealing with applications of: (a) Ni(II)-complexes of glycine as C-nucleophiles and (b) Ni(II)-complexes of dehydroalanine as Michael acceptors. The first group is significantly larger and consequently subdivided into four chapters based on the source of stereocontrolling element. Thus, a chiral auxiliary can be used as a part of nucleophilic glycine Ni(II) complex, Michael acceptor or both, leading to the conditions of matching vs. mismatching stereochemical preferences. The particular focus of the review is made on the practical aspects of the methodology under discussion and mechanistic considerations.

  8. N-phosphinyl imine chemistry (I): design and synthesis of novel N-phosphinyl imines and their application to asymmetric aza-Henry reaction.

    Science.gov (United States)

    Pindi, Suresh; Kaur, Parminder; Shakya, Gaurav; Li, Guigen

    2011-01-01

    Novel chiral N-phosphinamide and N-phosphinyl imines have been designed, synthesized and applied to asymmetric aza-Henry reaction to give excellent chemical yields (92%- quant.) and diastereoselectivity (91% to >99%de). The reaction showed a great substrate scope in which aromatic/aliphatic aldehyde- and ketone-derived N-phosphinyl imines can be employed as electrophiles. The chiral N-phosphinamide can be stored at room temperature for more than 2 months without inert gas protection, and chiral N-phosphinyl imines were also proven to be highly stable at room temperature for a long period under inert gas protection. The N-phosphinyl group enabled the product purification to be performed simply by washing crude product with EtOAc and hexane. This reaction joined other eight GAP (Group-Assistant-Purification) chemistry processes that were developed in our laboratories. The absolute configuration has been unambiguously determined by converting a β-nitroamine product into a known N-Boc sample. © 2010 John Wiley & Sons A/S.

  9. Asymmetrical reaction pathways for thermal and photocyclization of 1,3,5-hexatriene to 1,3-cyclohexadiene

    Energy Technology Data Exchange (ETDEWEB)

    Pichko, V.A.; Simkin, B.Ya.; Minkin, V.I.

    1987-08-01

    The theory of conservation of orbital symmetry in concerted reactions, outlined by Woodward and Hoffman, plays the dominant role in the prediction of the stereospecificity of these reactions both in the ground state and in excited states. Despite the importance of this theory with regard to preference for the conrotatory or dysrotatory pathway of cyclization, quantum chemical calculations of the critical portions of the potential energy surface of the ground and excited states become necessary in understanding the detailed mechanism of both thermal and photochemical transformations. The authors use these calculations to find, in the absence of symmetry, the potential energy surfaces of these states for 1,3,5-hexatriene and analyze the allowed and forbidden reaction pathways in its cyclization.

  10. Organocatalytic Asymmetric Domino Michael/Henry Reaction of Indolin-3-ones with o-Formyl-β-nitrostyrenes.

    Science.gov (United States)

    Mahajan, Suruchi; Chauhan, Pankaj; Loh, Charles C J; Uzungelis, Server; Raabe, Gerhard; Enders, Dieter

    2015-04-01

    A highly diastereo- and enantioselective domino Michael/Henry reaction of 1-acetylindolin-3-ones with o-formyl-(E)-β-nitrostyrenes catalyzed by low loading of a quinine-derived amine-squaramide provides the corresponding indolin-3-one derivatives bearing four adjacent stereogenic centers in good to high yields and with excellent stereoselectivities.

  11. Asymmetric nitrene transfer reactions: sulfimidation, aziridination and C-H amination using azide compounds as nitrene precursors.

    Science.gov (United States)

    Uchida, Tatsuya; Katsuki, Tsutomu

    2014-02-01

    Nitrogen functional groups are found in many biologically active compounds and their stereochemistry has a profound effect on biological activity. Nitrene transfer reactions such as aziridination, C-H bond amination, and sulfimidation are useful methods for introducing nitrogen functional groups, and the enantiocontrol of the reactions has been extensively investigated. Although high enantioselectivity has been achieved, most of the reactions use (N-arylsulfonylimino)phenyliodinane, which co-produces iodobenzene, as a nitrene precursor and have a low atom economy. Azide compounds, which give nitrene species by releasing nitrogen, are ideal precursors but rather stable. Their decomposition needs UV irradiation, heating in the presence of a metal complex, or Lewis acid treatment. The examples of previous azide decomposition prompted us to examine Lewis acid and low-valent transition-metal complexes as catalysts for azide decomposition. Thus, we designed new ruthenium complexes that are composed of a low-valent Ru(II) ion, apical CO ligand, and an asymmetry-inducing salen ligand. With these ruthenium complexes and azides, we have achieved highly enantioselective nitrene transfer reactions under mild conditions. Recently, iridium-salen complexes were added to our toolbox. Copyright © 2014 The Chemical Society of Japan and Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Asymmetric pathways in the electrochemical conversion reaction of NiO as battery electrode with high storage capacity

    Science.gov (United States)

    Boesenberg, Ulrike; Marcus, Matthew A.; Shukla, Alpesh K.; Yi, Tanghong; McDermott, Eamon; Teh, Pei Fen; Srinivasan, Madhavi; Moewes, Alexander; Cabana, Jordi

    2014-11-01

    Electrochemical conversion reactions of transition metal compounds create opportunities for large energy storage capabilities exceeding modern Li-ion batteries. However, for practical electrodes to be envisaged, a detailed understanding of their mechanisms is needed, especially vis-à-vis the voltage hysteresis observed between reduction and oxidation. Here, we present such insight at scales from local atomic arrangements to whole electrodes. NiO was chosen as a simple model system. The most important finding is that the voltage hysteresis has its origin in the differing chemical pathways during reduction and oxidation. This asymmetry is enabled by the presence of small metallic clusters and, thus, is likely to apply to other transition metal oxide systems. The presence of nanoparticles also influences the electrochemical activity of the electrolyte and its degradation products and can create differences in transport properties within an electrode, resulting in localized reactions around converted domains that lead to compositional inhomogeneities at the microscale.

  13. Asymmetric pathways in the electrochemical conversion reaction of NiO as battery electrode with high storage capacity.

    Science.gov (United States)

    Boesenberg, Ulrike; Marcus, Matthew A; Shukla, Alpesh K; Yi, Tanghong; McDermott, Eamon; Teh, Pei Fen; Srinivasan, Madhavi; Moewes, Alexander; Cabana, Jordi

    2014-11-20

    Electrochemical conversion reactions of transition metal compounds create opportunities for large energy storage capabilities exceeding modern Li-ion batteries. However, for practical electrodes to be envisaged, a detailed understanding of their mechanisms is needed, especially vis-à-vis the voltage hysteresis observed between reduction and oxidation. Here, we present such insight at scales from local atomic arrangements to whole electrodes. NiO was chosen as a simple model system. The most important finding is that the voltage hysteresis has its origin in the differing chemical pathways during reduction and oxidation. This asymmetry is enabled by the presence of small metallic clusters and, thus, is likely to apply to other transition metal oxide systems. The presence of nanoparticles also influences the electrochemical activity of the electrolyte and its degradation products and can create differences in transport properties within an electrode, resulting in localized reactions around converted domains that lead to compositional inhomogeneities at the microscale.

  14. 1,6-asymmetric induction in boron-mediated aldol reactions: application to a practical total synthesis of (+)-discodermolide.

    Science.gov (United States)

    Paterson, Ian; Delgado, Oscar; Florence, Gordon J; Lyothier, Isabelle; Scott, Jeremy P; Sereinig, Natascha

    2003-01-01

    By relying solely on substrate-based stereocontrol, a practical total synthesis of the microtubule-stabilizing anticancer agent (+)-discodermolide has been realized. This exploits a novel aldol bond construction with 1,6-stereoinduction from the boron enolate of (Z)-enone 3 in addition to aldehyde 2. The 1,3-diol 7 is employed as a common building block for the C(1)-C(5), C(9)-C(16), and C(17)-C(24) subunits. [reaction--see text

  15. A polystyrene-supported 9-amino(9-deoxy)epi quinine derivative for continuous flow asymmetric Michael reactions.

    Science.gov (United States)

    Izquierdo, Javier; Ayats, Carles; Henseler, Andrea H; Pericàs, Miquel A

    2015-04-14

    A polystyrene (PS)-supported 9-amino(9-deoxy)epi quinine derivative catalyzes Michael reactions affording excellent levels of conversion and enantioselectivity using different nucleophiles and structurally diverse enones. The highly recyclable, immobilized catalyst has been used to implement a single-pass, continuous flow process (residence time: 40 min) that can be operated for 21 hours without significant decrease in conversion and with improved enantioselectivity with respect to batch operation. The flow process has also been used for the sequential preparation of a small library of enantioenriched Michael adducts.

  16. Monomeric Cu(Ⅱ) Complex Containing Chiral Phase-transfer Catalyst as Ligand and Its Asymmetrically Catalytic Reaction

    Institute of Scientific and Technical Information of China (English)

    QU Zhi-Rong; XIONG Ren-Gen

    2008-01-01

    The thermal treatment of CuCl2 with N-(4'-vinylbenzyl)cinchonidinitim chloride(L1)afforded a monomeric discrete homochiral copper(Ⅱ)complex N-4'-(vinylbenzyl)cinchonidinium trichlorocoprate(Ⅱ)(1).Their applications to the enantioselectively catalytic alkylation reaction of N-(diphenylmethylidene)glycine tert-butyl ester(3)show that the higher ee value observed in catalyst 1 than that in the corresponding free ligand L1 is probably due to the rigidity enhancement after the coordination of N atom of quinoline ring to the copper ion.

  17. Mechanism and Stereoselectivity in an Asymmetric N-Heterocyclic Carbene-Catalyzed Carbon-Carbon Bond Activation Reaction.

    Science.gov (United States)

    Pareek, Monika; Sunoj, Raghavan B

    2016-11-18

    The mechanism and origin of stereoinduction in a chiral N-heterocyclic carbene (NHC) catalyzed C-C bond activation of cyclobutenone has been established using B3LYP-D3 density functional theory computations. The activation of cyclobutenone as an NHC-bound vinyl enolate and subsequent reaction with the electrophilic sulfonyl imine leads to the lactam product. The most preferred stereocontrolling transition state exhibits a number of noncovalent interactions rendering additional stabilization. The computed enantio- and diastereoselectivities are in good agreement with the previous experimental observations.

  18. Total synthesis of (+)-geldanamycin and (-)-o-quinogeldanamycin with use of asymmetric anti- and syn-glycolate aldol reactions.

    Science.gov (United States)

    Andrus, Merritt B; Meredith, Erik L; Simmons, Bryon L; Soma Sekhar, B B V; Hicken, Erik J

    2002-10-03

    Geldanamycin (GA), an antitumor Hsp90 inhibitor, was made for the first time by using an oxidative demethylation reaction as the final step. A biaryldioxanone auxiliary set the anti C11-12 hydroxy-methoxy functionality and a methylglycolate auxiliary based on norephedrine was used for the syn C6-7 methoxy-urethane. p-Quinone-forming oxidants, CAN and AgO, produced an unusual aza-quinone product. Nitric acid gave GA from a trimethoxy precursor in 55% yield as a 1:10 mixture with nonnatural o-quino-GA. [structure: see text

  19. Direct asymmetric vinylogous aldol reaction of allyl ketones with isatins: Divergent synthesis of 3-hydroxy-2-oxindole derivatives

    KAUST Repository

    Zhu, Bo

    2013-05-03

    6 in 1: The highly enantioselective title reaction is mediated by a bifunctional catalyst and leads to E-configured vinylogous aldol products (see scheme). These products are used as common intermediates in the synthesis of six biologically active 3-hydroxy-2-oxindole derivatives (e.g., CPC-1). Computational studies indicated that the observed stereoselectivity is a result of favorable secondary π-π* and H-bonding interactions in the transition state. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Multicatalyst system in asymmetric catalysis

    CERN Document Server

    Zhou, Jian

    2014-01-01

    This book introduces multi-catalyst systems by describing their mechanism and advantages in asymmetric catalysis.  Helps organic chemists perform more efficient catalysis with step-by-step methods  Overviews new concepts and progress for greener and economic catalytic reactions  Covers topics of interest in asymmetric catalysis including bifunctional catalysis, cooperative catalysis, multimetallic catalysis, and novel tandem reactions   Has applications for pharmaceuticals, agrochemicals, materials, and flavour and fragrance

  1. Mechanism, reactivity, and regioselectivity in rhodium-catalyzed asymmetric ring-opening reactions of oxabicyclic alkenes: a DFT Investigation

    Science.gov (United States)

    Qi, Zheng-Hang; Zhang, Yi; Gao, Yun; Zhang, Ye; Wang, Xing-Wang; Wang, Yong

    2017-01-01

    The origin of the enantio- and regioselectivity of ring-opening reaction of oxabicyclic alkenes catalyzed by rhodium/Josiphos has been examined using M06-2X density functional theory(DFT). DFT calculations predict a 98% ee for the enantioselectivity and only the 1,2-trans product as one regio- and diastereomer, in excellent agreement with experimental results. The solvent tetrahydrofuran(THF) plays a key role in assisting nucleophilic attack. Orbital composition analysis of the LUMO and the NPA atomic charge calculations were conducted to probe the origins of the regioselectivity. The orbital composition analysis reveals two potential electrophilic sites of the Rh–π-allyl intermediate M3 and the NPA atomic charges demonstrate that Cα carries more positive charges than Cγ, which suggests that Cα is the electrophilic site. PMID:28074930

  2. Mechanism, reactivity, and regioselectivity in rhodium-catalyzed asymmetric ring-opening reactions of oxabicyclic alkenes: a DFT Investigation

    Science.gov (United States)

    Qi, Zheng-Hang; Zhang, Yi; Gao, Yun; Zhang, Ye; Wang, Xing-Wang; Wang, Yong

    2017-01-01

    The origin of the enantio- and regioselectivity of ring-opening reaction of oxabicyclic alkenes catalyzed by rhodium/Josiphos has been examined using M06-2X density functional theory(DFT). DFT calculations predict a 98% ee for the enantioselectivity and only the 1,2-trans product as one regio- and diastereomer, in excellent agreement with experimental results. The solvent tetrahydrofuran(THF) plays a key role in assisting nucleophilic attack. Orbital composition analysis of the LUMO and the NPA atomic charge calculations were conducted to probe the origins of the regioselectivity. The orbital composition analysis reveals two potential electrophilic sites of the Rh-π-allyl intermediate M3 and the NPA atomic charges demonstrate that Cα carries more positive charges than Cγ, which suggests that Cα is the electrophilic site.

  3. Asymmetric cation-binding catalysis

    DEFF Research Database (Denmark)

    Oliveira, Maria Teresa; Lee, Jiwoong

    2017-01-01

    and KCN, are selectively bound to the catalyst, providing exceptionally high enantioselectivities for kinetic resolutions, elimination reactions (fluoride base), and Strecker synthesis (cyanide nucleophile). Asymmetric cation-binding catalysis was recently expanded to silicon-based reagents, enabling...... solvents, thus increasing their applicability in synthesis. The expansion of this concept to chiral polyethers led to the emergence of asymmetric cation-binding catalysis, where chiral counter anions are generated from metal salts, particularly using BINOL-based polyethers. Alkali metal salts, namely KF...

  4. Cyclodextrins in Asymmetric and Stereospecific Synthesis

    Directory of Open Access Journals (Sweden)

    Fliur Macaev

    2015-09-01

    Full Text Available Since their discovery, cyclodextrins have widely been used as green and easily available alternatives to promoters or catalysts of different chemical reactions in water. This review covers the research and application of cyclodextrins and their derivatives in asymmetric and stereospecific syntheses, with their division into three main groups: (1 cyclodextrins promoting asymmetric and stereospecific catalysis in water; (2 cyclodextrins’ complexes with transition metals as asymmetric and stereospecific catalysts; and (3 cyclodextrins’ non-metallic derivatives as asymmetric and stereospecific catalysts. The scope of this review is to systematize existing information on the contribution of cyclodextrins to asymmetric and stereospecific synthesis and, thus, to facilitate further development in this direction.

  5. Chiral ionic liquid/ESI-MS methodology as an efficient tool for the study of transformations of supported organocatalysts: deactivation pathways of Jørgensen-Hayashi-type catalysts in asymmetric Michael reactions.

    Science.gov (United States)

    Maltsev, Oleg V; Chizhov, Alexander O; Zlotin, Sergei G

    2011-05-23

    The deactivation pathways of Jørgensen-Hayashi-type organocatalysts modified with an ionic liquid fragment in asymmetric Michael reactions of α,β-enals with C- (nitromethane, dimethylmalonate) or N-nucleophiles (N-carbobenzyloxyhydroxylamine) that involved an iminium-ion formation step were studied for the first time by the electrospray ionization mass spectrometry (ESI-MS). "Parasitic" side reactions and undesirable cation intermediates that poisoned the catalysts were identified in accordance with their m/z values as well as their relation to the reported mechanisms of Michael reactions in the presence of O-TMS-α,α-diarylprolinol (TMS=trimethylsilyl) derivatives. The proposed approach may be useful for the study of transformations of other types of organocatalysts modified with ionic groups in various organocatalytic reactions and for the development of novel robust catalysts and processes that would be suitable for large-scale industrial applications.

  6. Ruthenium and osmium complexes of hemilabile chiral monophosphinite ligands derived from 1D-pinitol or 1D-chiro-inositol as catalysts for asymmetric hydrogenation reactions.

    Science.gov (United States)

    Slade, Angela T; Lensink, Cornelis; Falshaw, Andrew; Clark, George R; Wright, L James

    2014-12-07

    The monophosphinite ligands, 1D-1,2;5,6-di-O-cyclopentylidene-3-O-methyl-4-O-diphenylphosphino-chiro-inositol (D-P1), 1D-1,2;5,6-di-O-isopropylidene-3-O-methyl-4-O-diphenylphosphino-chiro-inositol (D-P2), 1D-1,2;5,6-di-O-cyclohexylidene-3-O-methyl-4-O-diphenylphosphino-chiro-inositol (D-P3), and 1D-1,2;5,6-di-O-cyclopentylidene-3-O-ethyl-4-O-diphenylphosphino-chiro-inositol (D-P4), can be conveniently prepared from the chiral natural products 1D-pinitol or 1D-chiro-inositol. On treatment of toluene solutions of RuCl2(PPh3)3 with two mole equivalents of the ligands D-PY (Y = 1-4) the complexes RuCl2(D-P1)2 (1), RuCl2(D-P2)2 (4), RuCl2(D-P3)2 (5), or RuCl2(D-P4)2 (6), respectively, are formed. Similarly, treatment of OsCl2(PPh3)3 with D-P1 gives OsCl2(D-P1)2 (7). The single crystal X-ray structure determination of 1 reveals that each D-P1 ligand coordinates to ruthenium through phosphorus and the oxygen atom of the methoxyl group. Treatment of 1 with excess LiBr or LiI results in metathesis of the chloride ligands and RuBr2(D-P1)2 (2) or RuI2(D-P1)2 (3), respectively, are formed. Exposure of a solution of 1 to carbon monoxide results in the very rapid formation of RuCl2(CO)2(D-P1)2 (8), thereby demonstrating the ease with which the oxygen donors are displaced from the metal and hence the hemilabile nature of the two bidentate D-P1 ligands in 1. Preliminary studies indicate that 1-7 act as catalysts for the asymmetric hydrogenation reactions of acetophenone and 3-quinuclidinone to give the corresponding alcohols in generally high conversions but low enantiomeric excesses.

  7. Selector-induced dynamic deracemization of a selectand-modified tropos BIPHEPO-ligand: application in the organocatalyzed asymmetric double-aldol-reaction.

    Science.gov (United States)

    Maier, Frank; Trapp, Oliver

    2014-08-11

    Stereolabile interconverting catalysts open up the possibility of directing enantioselectivity in asymmetric synthesis by formation of diastereomeric complexes with chiral auxiliaries and deracemization. However, the stoichiometrically used auxilliaries can significantly limit the potential applications of such systems. We synthesized a new BIPHEPO tropos ligand containing achiral selectands in the backbone, which forms transient diastereomeric associates with amylose-tris-3,5-dimethylphenyl carbamate as a selector and thus deracemizes. The enantiomerically enriched BIPHEPO obtained was successfully used in the organocatalytic asymmetric double aldol addition of substituted methyl ketones to form benzaldehyde. This strategy combines an on-column deracemization with the high stereoinduction of chiral biarylphosphineoxides and opens up new possibilities in the field of self-amplified asymmetric syntheses. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Asymmetric synthesis of α-amino acids via homologation of Ni(II) complexes of glycine Schiff bases. Part 2: aldol, Mannich addition reactions, deracemization and (S) to (R) interconversion of α-amino acids.

    Science.gov (United States)

    Sorochinsky, Alexander E; Aceña, José Luis; Moriwaki, Hiroki; Sato, Tatsunori; Soloshonok, Vadim

    2013-11-01

    This review provides a comprehensive treatment of literature data dealing with asymmetric synthesis of α-amino-β-hydroxy and α,β-diamino acids via homologation of chiral Ni(II) complexes of glycine Schiff bases using aldol and Mannich-type reactions. These reactions proceed with synthetically useful chemical yields and thermodynamically controlled stereoselectivity and allow direct introduction of two stereogenic centers in a single operation with predictable stereochemical outcome. Furthermore, new application of Ni(II) complexes of α-amino acids Schiff bases for deracemization of racemic α-amino acids and (S) to (R) interconversion providing additional synthetic opportunities for preparation of enantiomerically pure α-amino acids, is also reviewed. Origin of observed diastereo-/enantioselectivity in the aldol, Mannich-type and deracemization reactions, generality and limitations of these methodologies are critically discussed.

  9. Chemoenzymatic asymmetric total syntheses of antitumor agents (3R,9R,10R)- and (3S,9R,10R)-Panaxytriol and (R)- and (S)-Falcarinol from Panax ginseng using an enantioconvergent enzyme-triggered cascade reaction.

    Science.gov (United States)

    Mayer, Sandra F; Steinreiber, Andreas; Orru, Romano V A; Faber, Kurt

    2002-12-27

    Total asymmetric synthesis of two components of Panax ginseng showing antitumor activity, i.e., (3R,9R,10R)- and (3S,9R,10R)-Panaxytriol and of both enantiomers of Falcarinol was accomplished. Due to the fact that the synthetic strategy was based on enantioconvergent biotransformations, the occurrence of any undesired stereoisomer was entirely avoided. The absolute configuration of naturally occurring Panaxytriol was confirmed to be (3R,9R,10R) on the basis of optical rotation values. It was shown that enzyme-triggered cascade reactions represent a valuable tool for the synthesis of natural products.

  10. Asymmetric catalysis : ligand design and microwave acceleration

    OpenAIRE

    Bremberg, Ulf

    2000-01-01

    This thesis deals partly with the design and synthesis ofligands for use in asymmetric catalysis, and partly with theapplication of microwave heating on metal-based asymmetriccatalytic reactions. Enantiomerically pure pyridyl alcohols and bipyridylalcohols were synthesized from the chiral pool for future usein asymmetric catalysis. Lithiated pyridines were reacted withseveral chiral electrophiles, yielding diastereomeric mixturesthat could be separated without the use of resolutiontechniques....

  11. Mechanochemistry assisted asymmetric organocatalysis: A sustainable approach

    Directory of Open Access Journals (Sweden)

    Pankaj Chauhan

    2012-12-01

    Full Text Available Ball-milling and pestle and mortar grinding have emerged as powerful methods for the development of environmentally benign chemical transformations. Recently, the use of these mechanochemical techniques in asymmetric organocatalysis has increased. This review highlights the progress in asymmetric organocatalytic reactions assisted by mechanochemical techniques.

  12. Mechanochemistry assisted asymmetric organocatalysis: A sustainable approach.

    Science.gov (United States)

    Chauhan, Pankaj; Chimni, Swapandeep Singh

    2012-01-01

    Ball-milling and pestle and mortar grinding have emerged as powerful methods for the development of environmentally benign chemical transformations. Recently, the use of these mechanochemical techniques in asymmetric organocatalysis has increased. This review highlights the progress in asymmetric organocatalytic reactions assisted by mechanochemical techniques.

  13. Measurement of Cross Sections for the 10B(n,α)'7Li Reaction at 4.0 and 5.0 MeV Using an Asymmetrical Twin Gridded Ionization Chamber

    Institute of Scientific and Technical Information of China (English)

    ZHANG Guo-Hui; LIU Xiang; LIU Jia-Ming; XUE Zhi-Hua; WU Hao; CHEN Jin-Xiang

    2011-01-01

    @@ Cross sections of the 10B(n, α) 7Li reaction (including the total, the "leaking" alpha, forward alpha and backward alpha parts) at En=4.0 and 5.OMcV were measured using an asymmetrical twin gridded ionization chamber and two back-to-back 10B samples.Measurements were performed at the 4.5MV Van de Graaff accelerator of Peking University.Monoenergetic neutrons were produced through the 2H(d, n)3 He reaction with a deuterium gas target.Absolute neutron flux was determined by a 238 U sample set inside the gridded ionization chamber and a BF3 long counter was employed as a neutron flux monitor and for normalization.The present results are compared with previous measurements and evaluations.

  14. Enantiopure sulfoxides: recent applications in asymmetric synthesis.

    Science.gov (United States)

    Carreño, M Carmen; Hernández-Torres, Gloria; Ribagorda, María; Urbano, Antonio

    2009-11-07

    Sulfoxides are nowadays recognised as powerful chiral auxiliaries that may participate in a wide range of asymmetric reactions. Their high configurational stability, the existence of several efficient methods allowing the access to both configurations as well as their synthetic versatility are characteristic features offering a tremendous potential to develop new applications. Significant recent advances leading to high asymmetric inductions in carbon-carbon and carbon-oxygen bond forming reactions, and applications of homochiral sulfoxides to atroposelective synthesis and asymmetric catalysis are discussed. New uses of sulfoxides in the design of chiroptical switches are also shown.

  15. Synthesis of 3,3-Disubstituted Oxindoles by Palladium-Catalyzed Asymmetric Intramolecular α-Arylation of Amides: Reaction Development and Mechanistic Studies.

    Science.gov (United States)

    Katayev, Dmitry; Jia, Yi-Xia; Sharma, Akhilesh K; Banerjee, Dipshikha; Besnard, Céline; Sunoj, Raghavan B; Kündig, E Peter

    2013-09-02

    Palladium complexes incorporating chiral N-heterocyclic carbene (NHC) ligands catalyze the asymmetric intramolecular α-arylation of amides producing 3,3-disubstituted oxindoles. Comprehensive DFT studies have been performed to gain insight into the mechanism of this transformation. Oxidative addition is shown to be rate-determining and reductive elimination to be enantioselectivity-determining. The synthesis of seven new NHC ligands is detailed and their performance is compared. One of them, L8, containing a tBu and a 1-naphthyl group at the stereogenic centre, proved superior and was very efficient in the asymmetric synthesis of fifteen new spiro-oxindoles and three azaspiro-oxindoles often in high yields (up to 99 %) and enantioselectivities (up to 97 % ee; ee=enantiomeric excess). Three palladacycle intermediates resulting from the oxidative addition of [Pd(NHC)] into the aryl halide bond were isolated and structurally characterized (X-ray). Using these intermediates as catalysts showed alkene additives to play an important role in increasing turnover number and frequency.

  16. Nonlinear effects in asymmetric catalysis.

    Science.gov (United States)

    Satyanarayana, Tummanapalli; Abraham, Susan; Kagan, Henri B

    2009-01-01

    There is a need for the preparation of enantiomerically pure compounds for various applications. An efficient approach to achieve this goal is asymmetric catalysis. The chiral catalyst is usually prepared from a chiral auxiliary, which itself is derived from a natural product or by resolution of a racemic precursor. The use of non-enantiopure chiral auxiliaries in asymmetric catalysis seems unattractive to preparative chemists, since the anticipated enantiomeric excess (ee) of the reaction product should be proportional to the ee value of the chiral auxiliary (linearity). In fact, some deviation from linearity may arise. Such nonlinear effects can be rich in mechanistic information and can be synthetically useful (asymmetric amplification). This Review documents the advances made during the last decade in the use of nonlinear effects in the area of organometallic and organic catalysis.

  17. A dual arylboronic acid--aminothiourea catalytic system for the asymmetric intramolecular hetero-Michael reaction of α,β-unsaturated carboxylic acids.

    Science.gov (United States)

    Azuma, Takumi; Murata, Akihiro; Kobayashi, Yusuke; Inokuma, Tsubasa; Takemoto, Yoshiji

    2014-08-15

    A bifunctional aminoboronic acid has been used to facilitate for the first time the intramolecular aza- and oxa-Michael reactions of α,β-unsaturated carboxylic acids. The combination of an arylboronic acid with a chiral aminothiourea allowed for these reactions to proceed successfully in an enantioselective manner to afford the desired heterocycles in high yields and ee's (up to 96% ee). The overall utility of this dual catalytic system was demonstrated by a one-pot enantioselective synthesis of (+)-erythrococcamide B, which proceeded via sequential Michael and amidation reactions.

  18. Chiral Pd aqua complex-catalyzed asymmetric C-C bond-forming reactions: a Brønsted acid-base cooperative system.

    Science.gov (United States)

    Sodeoka, Mikiko; Hamashima, Yoshitaka

    2009-10-21

    Chiral cationic Pd aqua complexes can function as acid-base catalysts, effectively activating active methylene and methine compounds to give chiral Pd enolates. It is noteworthy that such enolate formation occurs with concomitant formation of a strong protic acid. Although the reactivity of the Pd enolate itself is not sufficient for reactions with carbon-based electrophiles, its cooperative action with the protic acid to activate the electrophiles allows the desired C-C bond-forming reactions to proceed smoothly in a highly enantioselective manner. Based on this mechanistic feature, reactions with acetals have been developed; these are difficult to achieve using conventional basic enolate chemistry.

  19. 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

    2015-06-02

    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.

  20. Can the analyte-triggered asymmetric autocatalytic Soai reaction serve as a universal analytical tool for measuring enantiopurity and assigning absolute configuration?

    Science.gov (United States)

    Welch, Christopher J; Zawatzky, Kerstin; Makarov, Alexey A; Fujiwara, Satoshi; Matsumoto, Arimasa; Soai, Kenso

    2016-12-20

    An investigation is reported on the use of the autocatalytic enantioselective Soai reaction, known to be influenced by the presence of a wide variety of chiral materials, as a generic tool for measuring the enantiopurity and absolute configuration of any substance. Good generality for the reaction across a small group of test analytes was observed, consistent with literature reports suggesting a diversity of compound types that can influence the stereochemical outcome of this reaction. Some trends in the absolute sense of stereochemical enrichment were noted, suggesting the possible utility of the approach for assigning absolute configuration to unknown compounds, by analogy to closely related species with known outcomes. Considerable variation was observed in the triggering strength of different enantiopure materials, an undesirable characteristic when dealing with mixtures containing minor impurities with strong triggering strength in the presence of major components with weak triggering strength. A strong tendency of the reaction toward an 'all or none' type of behavior makes the reaction most sensitive for detecting enantioenrichment close to zero. Consequently, the ability to discern modest from excellent enantioselectivity was relatively poor. While these properties limit the ability to obtain precise enantiopurity measurements in a simple single addition experiment, prospects may exist for more complex experimental setups that may potentially offer improved performance.

  1. Asymmetric Ashes

    Science.gov (United States)

    2006-11-01

    that oscillate in certain directions. Reflection or scattering of light favours certain orientations of the electric and magnetic fields over others. This is why polarising sunglasses can filter out the glint of sunlight reflected off a pond. When light scatters through the expanding debris of a supernova, it retains information about the orientation of the scattering layers. If the supernova is spherically symmetric, all orientations will be present equally and will average out, so there will be no net polarisation. If, however, the gas shell is not round, a slight net polarisation will be imprinted on the light. This is what broad-band polarimetry can accomplish. If additional spectral information is available ('spectro-polarimetry'), one can determine whether the asymmetry is in the continuum light or in some spectral lines. In the case of the Type Ia supernovae, the astronomers found that the continuum polarisation is very small so that the overall shape of the explosion is crudely spherical. But the much larger polarization in strongly blue-shifted spectral lines evidences the presence, in the outer regions, of fast moving clumps with peculiar chemical composition. "Our study reveals that explosions of Type Ia supernovae are really three-dimensional phenomena," says Dietrich Baade. "The outer regions of the blast cloud is asymmetric, with different materials found in 'clumps', while the inner regions are smooth." "This study was possible because polarimetry could unfold its full strength thanks to the light-collecting power of the Very Large Telescope and the very precise calibration of the FORS instrument," he adds. The research team first spotted this asymmetry in 2003, as part of the same observational campaign (ESO PR 23/03 and ESO PR Photo 26/05). The new, more extensive results show that the degree of polarisation and, hence, the asphericity, correlates with the intrinsic brightness of the explosion. The brighter the supernova, the smoother, or less clumpy

  2. Absolute Asymmetric Synthesis Using A Cocrystal Approach

    Institute of Scientific and Technical Information of China (English)

    H.Koshima

    2007-01-01

    1 Results Absolute asymmetric synthesis by means of solid-state reaction of chiral crystals self-assembled from achiral molecules is an attractive and promising methodology for asymmetric synthesis because it is not necessary to employ any external chiral source like a chiral catalyst.In order to design reliably absolute asymmetric syntheses in the solid state,it is inevitable to prepare and predict the formation of chiral crystals from achiral compounds.We have prepared a number of chiral cocrystals co...

  3. Asymmetric Ketone Reduction by Imine Reductases.

    Science.gov (United States)

    Lenz, Maike; Meisner, Jan; Quertinmont, Leann; Lutz, Stefan; Kästner, Johannes; Nestl, Bettina M

    2017-02-01

    The rapidly growing area of asymmetric imine reduction by imine reductases (IREDs) has provided alternative routes to chiral amines. Here we report the expansion of the reaction scope of IREDs by showing the stereoselective reduction of 2,2,2-trifluoroacetophenone. Assisted by an in silico analysis of energy barriers, we evaluated asymmetric hydrogenations of carbonyls and imines while considering the influence of substrate reactivity on the chemoselectivity of this novel class of reductases. We report the asymmetric reduction of C=N as well as C=O bonds catalysed by members of the IRED enzyme family. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Asymmetric Synthesis of Bicyclic Nitrocyclopropanes from Primary Nitro Compounds and Stereoselective Formation of Tetrahydro-2H-cyclopenta[b]furans via Ring Expansion/Cyclization Reaction.

    Science.gov (United States)

    Kamimura, Akio; Moriyama, Takaaki; Ito, Yuji; Kawamoto, Takuji; Uno, Hidemitsu

    2016-06-03

    Optically active bicyclic nitrocyclopropanes are readily prepared from primary chiral nitro compounds, prepared by the conjugate addition of propionaldehyde to a nitro alkene in the presence of proline-derived organocatalysts. The one-step cyclopropanation took place smoothly in a highly stereoselective manner regardless of the stereogenic center adjacent to the allylic unit. Although the allylation reaction catalyzed by BF3·OEt2 provides a mixture of two possible diastereomers, subsequent oxidation of the alcoholic carbon after the formation of nitrocyclopropanes gave diastereomerically pure single products. As a result, separation of the diastereomers during the reaction sequence is unnecessary. Baeyer-Villiger oxidation of the bicyclic nitrocyclopropane ketones followed by enolization resulted in stereoselective formation of a novel cyclopenta[b]furan ring in good yield via ring expansion followed by transannular nucleophilic cyclization.

  5. 金鸡纳碱及其衍生物在不对称Mannich反应中的应用%Application of Cinchona Alkaloid and their Derivatives in Asymmetric Mannich Reactions

    Institute of Scientific and Technical Information of China (English)

    潘昭喜; 何永光; 刘浩

    2012-01-01

    Catalytic enantioselective Mannich reactions provided one of the most versatile approaches for the synthesis of optically active chiral amines.Recently,several organocatalytic protocols were developed by using the parent cinchona alkaloids or their derivatives.It was a focus of considerable attention in the domestic and foreign research.The recent progress of asymmetric Mannich reactions catalyzed by cinchona alkaloids or their derivatives was generally reviewed.%不对称Mannich反应是一种应用最广泛的合成光学活性的手性氨基酸衍生物的方法,近几年基于金鸡纳碱及其衍生物的有机小分子催化的不对称Mannich反应成为国内外研究的热点,本文简要介绍了金鸡纳碱及其衍生物在不对称Mannich反应中的应用。

  6. Asymmetric NHC-catalyzed aza-Diels-Alder reactions: Highly enantioselective route to α-amino acid derivatives and DFT calculations

    KAUST Repository

    Yang, Limin

    2014-08-01

    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.

  7. Combining Organocatalysis and Lanthanide Catalysis: A Sequential One-Pot Quadruple Reaction Sequence/Hetero-Diels-Alder Asymmetric Synthesis of Functionalized Tricycles.

    Science.gov (United States)

    Dochain, Simon; Vetica, Fabrizio; Puttreddy, Rakesh; Rissanen, Kari; Enders, Dieter

    2016-12-23

    A stereoselective one-pot synthesis of functionalized complex tricyclic polyethers has been achieved using the combination of secondary amine and lanthanide catalysis. This one-pot quadruple reaction/Hetero-Diels-Alder sequence gave good yields (per step) as well as excellent diastereo- and enantioselectivities. Furthermore, the particular combination of lanthanide complexes with organocatalysis is one of the first examples described for sequential catalysis. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. The direct asymmetric vinylogous aldol reaction of furanones with α-ketoesters: Access to chiral γ-Butenolides and glycerol derivatives

    KAUST Repository

    Luo, Jie

    2011-01-11

    Twice as good: The title reaction using the tryptophan-derived bifunctional organic catalyst 1 has been developed. The reported method led to the synthesis of chiral γ-substituted butenolides in excellent yields, with high diastereo- and enantioselectivities. Facile synthesis of chiral glycerol derivatives containing a tertiary hydroxy group has also been demonstrated. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Synthesis, Characterization, and Crystal Structure of a Novel Copper(II) Complex with an Asymmetric Coordinated 2,2'-Bipyridine Derivative: A Model for the Associative Complex in the Ligand-Substitution Reactions of [Cu(tren)L](2+)?

    Science.gov (United States)

    Lu Zl, Zhong-lin; Duan Cy, Chun-ying; Tian Yp, Yu-peng; You Xz, Xiao-zeng; Huang Xy, Xiao-ying

    1996-04-10

    The titled compound, (tris(2-aminoethyl)amine)(4,5-diazafluoren-9-one) copper(II) perchlorate, [Cu(C(6)H(18)N(4))(C(11)H(6)N(2)O)(ClO(4))(2)], 1, has been designed, synthesized, and characterized. The electronic and ESR spectra are very different from those of [Cu(tren)L](2+) complexes where L is monodentate ligand. The X-ray analysis revealed that the complex crystallizes in the monoclinic space group P2(1)/c, with a = 10.726(6) Å, b = 14.921(7) Å, c = 14.649(4) Å, beta = 95.13(3) degrees, and Z = 4. The copper(II) ion is coordinated by four nitrogen atoms from tris(2-aminoethyl)amine (tren) and two nitrogen atoms from 4,5-diazafluoren-9-one (dzf) to form an unusual six-coordinate (4 + 1 + 1') geometry. The structure is very rare, and to our knowledge, it is the first example of an asymmetric bidentate phenanthroline derivative metal complex. The structure could be used as a model of the associative complex in the ligand-exchange and ligand-substitution reactions of [Cu(tren)L](2+) and the catalytic mechanisms of enzymes involving copper sites. From the electronic and variable-temperature ESR spectra in solution, the possible mechanism of these reactions has also been proposed. As a comparison, the complex [Cu(tren)(ImH)(ClO(4))(2)], 2, was also synthesized and characterized, where ImH is imidazole.

  10. Asymmetric catalytic synthesis of the proposed structure of trocheliophorolide B.

    Science.gov (United States)

    Trost, Barry M; Quintard, Adrien

    2012-09-01

    A concise catalytic asymmetric synthesis of the proposed structure of trocheliophorolide B is reported. The synthetic sequence notably features an asymmetric acetaldehyde alkynylation, a Ru-catalyzed alder-ene reaction, and a Zn-ProPhenol ynone aldol condensation. Comparison with the reported data suggests a misassignment of the natural product structure.

  11. Asymmetric Synthesis of (+)-(11 R,12S)-Mefloquine Hydrochloride

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    The asymmetric synthesis of (+)-(11R,12S)-mefloquine hydrochloride, an antimalarial drug, was accomplished from commercially available 2-trifluoromethylaniline, ethyl 4,4,4-trifluoroacetoacetate and cyclopentanone in 7 steps with a 14% overall yield. The key steps were proline-catalyzed asymmetric direct aldol reaction and Beck-mann rearrangement. The absolute configuration was assigned by a Mosher's method.

  12. 不对称结构双核铜(I)配合物的合成、反应与荧光光谱%Synthesis, Reaction and Luminescence of Asymmetric Binuclear Copper(I) Complex

    Institute of Scientific and Technical Information of China (English)

    赵东; 孙雨安; 刘应凡; 张传建

    2005-01-01

      Asymmetric binuclear copper(I) complex has been synthesized by the reaction between [Cu(dppm)(ClO4)]2 and 4-vinylpyridine [dppm= bis(diphenylphosphino) methane, C7H7N=4-vinylpyridine] and characterized by specific elemental analyses, 31P NMR and luminescence analysis. The X-ray crystal structure of the title complex shows that dppm and acetylide coordinate as bridging bidentate ligands to the Cu(I) atoms, and 4-vinylpyridine as monodentate ligand. The ClO4- ion is free in the newly prepared binuclear copper(I) complex.%  通过配位催化反应首次合成了含双二苯基膦甲烷(dppm)和4-乙烯吡啶(C7H7N)混合配体的具有不对称结构双核铜(I)配合物[Cu2(dppm)2(CH2=CH-C5H4N)2(µ-C≡CH)](ClO4),并经X射线结构分析和荧光光谱表征了配合物的结构特征。结构分析表明,dppm 作为桥式双齿配体、4-乙烯吡啶作为单齿配体,小分子乙炔以桥式配位分别与铜原子形成四面体配位结构,高氯酸根离子位于配合物外界。

  13. Chiral Brønsted Acids for Asymmetric Organocatalysis

    Science.gov (United States)

    Kampen, Daniela; Reisinger, Corinna M.; List, Benjamin

    Chiral Brønsted acid catalysis is an emerging area of organocatalysis. Since the pioneering studies of the groups of Akiyama and Terada in 2004 on the use of chiral BINOL phosphates as powerful Brønsted acid catalysts in asymmetric Mannich-type reactions, numerous catalytic asymmetric transformations involving imine activation have been realized by means of this catalyst class, including among others Friedel-Crafts, Pictet-Spengler, Strecker, cycloaddition reactions, transfer hydrogenations, and reductive aminations. More recently, chiral BINOL phosphates found application in multicomponent and cascade reactions as for example in an asymmetric version of the Biginelli reaction. With the introduction of chiral BINOL-derived N-triflyl phosphoramides in 2006, asymmetric Brønsted acid catalysis is no longer restricted to reactive substrates. Also certain carbonyl compounds can be activated through these stronger Brønsted acid catalysts. In dealing with sensitive substrate classes, chiral dicarboxylic acids proved of particular value.

  14. Synthesis of asymmetric tetracarboxylic acids and corresponding dianhydrides

    Science.gov (United States)

    Chuang, Chun-Hua (Inventor)

    2008-01-01

    This invention relates to processes for preparing asymmetrical biphenyl tetracarboxylic acids and the corresponding asymmetrical dianhydrides, namely 2,3,3',4'-biphenyl dianhydride (a-BPDA), 2,3,3',4'-benzophenone dianhydride (a-BTDA) and 3,4'-methylenediphthalic anhydride (-MDPA). By cross-coupling reactions of reactive metal substituted o-xylenes or by cross-coupling o-xylene derivatives in the presence of catalysts, this invention specifically produces asymmetrical biphenyl intermediates that are subsequently oxidized or hydrolyzed and oxidized to provide asymmetric biphenyl tetracarboxylic acids in comparatively high yields. These asymmetrical biphenyl tetracarboxylic acids are subsequently converted to the corresponding asymmetrical dianhydrides without contamination by symmetrical biphenyl dianhydrides.

  15. Asymmetric catalysis with short-chain peptides.

    Science.gov (United States)

    Lewandowski, Bartosz; Wennemers, Helma

    2014-10-01

    Within this review article we describe recent developments in asymmetric catalysis with peptides. Numerous peptides have been established in the past two decades that catalyze a wide variety of transformations with high stereoselectivities and yields, as well as broad substrate scope. We highlight here catalytically active peptides, which have addressed challenges that had thus far remained elusive in asymmetric catalysis: enantioselective synthesis of atropoisomers and quaternary stereogenic centers, regioselective transformations of polyfunctional substrates, chemoselective transformations, catalysis in-flow and reactions in aqueous environments.

  16. Homogeneous asymmetric catalysis in fragrance chemistry.

    Science.gov (United States)

    Ciappa, Alessandra; Bovo, Sara; Bertoldini, Matteo; Scrivanti, Alberto; Matteoli, Ugo

    2008-06-01

    Opposite enantiomers of a chiral fragrance may exhibit different olfactory activities making a synthesis in high enantiomeric purity commercially and scientifically interesting. Accordingly, the asymmetric synthesis of four chiral odorants, Fixolide, Phenoxanol, Citralis, and Citralis Nitrile, has been investigated with the aim to develop practically feasible processes. In the devised synthetic schemes, the key step that leads to the formation of the stereogenic center is the homogeneous asymmetric hydrogenation of a prochiral olefin. By an appropriate choice of the catalyst and the reaction conditions, Phenoxanol, Citralis, and Citralis Nitrile were obtained in high enantiomeric purity, and odor profiles of the single enantiomers were determined.

  17. Cold asymmetrical fermion superfluids

    Energy Technology Data Exchange (ETDEWEB)

    Caldas, Heron

    2003-12-19

    The recent experimental advances in cold atomic traps have induced a great amount of interest in fields from condensed matter to particle physics, including approaches and prospects from the theoretical point of view. In this work we investigate the general properties and the ground state of an asymmetrical dilute gas of cold fermionic atoms, formed by two particle species having different densities. We have show in a recent paper, that a mixed phase composed of normal and superfluid components is the energetically favored ground state of such a cold fermionic system. Here we extend the analysis and verify that in fact, the mixed phase is the preferred ground state of an asymmetrical superfluid in various situations. We predict that the mixed phase can serve as a way of detecting superfluidity and estimating the magnitude of the gap parameter in asymmetrical fermionic systems.

  18. Asymmetrical field emitter

    Science.gov (United States)

    Fleming, J.G.; Smith, B.K.

    1995-10-10

    A method is disclosed for providing a field emitter with an asymmetrical emitter structure having a very sharp tip in close proximity to its gate. One preferred embodiment of the present invention includes an asymmetrical emitter and a gate. The emitter having a tip and a side is coupled to a substrate. The gate is connected to a step in the substrate. The step has a top surface and a side wall that is substantially parallel to the side of the emitter. The tip of the emitter is in close proximity to the gate. The emitter is at an emitter potential, and the gate is at a gate potential such that with the two potentials at appropriate values, electrons are emitted from the emitter. In one embodiment, the gate is separated from the emitter by an oxide layer, and the emitter is etched anisotropically to form its tip and its asymmetrical structure. 17 figs.

  19. Asymmetric synthesis of the dibenzocyclooctadiene lignans interiotherin a and gomisin R.

    Science.gov (United States)

    Coleman, Robert S; Gurrala, Srinivas Reddy

    2005-04-28

    [structure: see text] Asymmetric total syntheses of the dibenzocyclooctadiene lignans interiotherin A and angeloylgomisin R are reported. The syntheses were based on an atropdiastereoselective, copper-promoted biaryl coupling reaction, a diastereoselective hydroboration/Suzuki-Miyaura coupling reaction sequence, and an asymmetric boron-mediated tiglylation of an aryl aldehyde precursor.

  20. Recent Advances in Substrate-Controlled Asymmetric Cyclization for Natural Product Synthesis

    Directory of Open Access Journals (Sweden)

    Jeyun Jo

    2017-06-01

    Full Text Available Asymmetric synthesis of naturally occurring diverse ring systems is an ongoing and challenging research topic. A large variety of remarkable reactions utilizing chiral substrates, auxiliaries, reagents, and catalysts have been intensively investigated. This review specifically describes recent advances in successful asymmetric cyclization reactions to generate cyclic architectures of various natural products in a substrate-controlled manner.

  1. Asymmetric total synthesis of vindoline.

    Science.gov (United States)

    Kato, Daisuke; Sasaki, Yoshikazu; Boger, Dale L

    2010-03-24

    A concise asymmetric total synthesis of (-)-vindoline (1) is detailed based on a tandem intramolecular [4+2]/[3+2] cycloaddition cascade of a 1,3,4-oxadiazole inspired by the natural product structure, in which the tether linking the initiating dienophile and oxadiazole bears a chiral substituent that controls the facial selectivity of the initiating Diels-Alder reaction and sets absolute stereochemistry of the remaining six stereocenters in the cascade cycloadduct. This key reaction introduces three rings and four C-C bonds central to the pentacyclic ring system setting all six stereocenters and introducing essentially all the functionality found in the natural product in a single step. Implementation of the approach also required the development of a unique ring expansion reaction to provide a six-membered ring suitably functionalized for introduction of the Delta (6, 7)-double bond found in the core structure of vindoline and defined our use of a protected hydroxymethyl group as the substituent used to control the stereochemical course of the cycloaddition cascade.

  2. Monoterpenos di-hidroxilados e hidróxi-nitrogenados 1,2 e 1,3 como ligantes quirais em reação de reformatsky assimétrica 1,2- and 1,3-dihydroxylated and hydroxynitrogenated monoterpenes as chiral ligands in the asymmetric reformatsky reaction

    Directory of Open Access Journals (Sweden)

    Carlos Magno R. Ribeiro

    2008-01-01

    Full Text Available This study describes the use of three (--alpha-pinene derivatives, one diol-1,2 [(--(1R, 2R, 3S, 5R-2,6,6-trimethylbicyclo[3.1.1]heptane-2,3-diol 4] and two piridine-hydroxy derivatives [(+-(1R,2S,3R,5S-2,6,6-trimethyl-3-(2-pyridinylmethylbicyclo[3.1.1]heptan-3-ol 7 and (--(1R,2S,3R,5S-2,6,6-trimethyl-3-[2-(2-pyridinyl ethyl]bicyclo[3.1.1]heptan-3-ol 8]; one diol-1,3 [(--(1S,2R,5S-2-(1-hydroxy-1-methylethyl-5-methylcyclohexanol 5] derived from (+-isopulegol 2 and one diol-1,3 [(+-(1R,2R,5R-2-(1-hydroxy-1-methylethyl-5-methylcyclohexanol 6] derived from (+-neo-isopulegol 3, as ligands in the asymmetric Reformatsky reaction. The best enantiomeric excess of beta-hydroxy ester obtained in the Reformatsky asymmetric reaction was 18% using ligand 6, and the chemical yield of the reactions was 65% on average.

  3. 1,2- and 1,3-dihydroxylated and hydroxynitrogenated monoterpenes as chiral ligands in the asymmetric reformatsky reaction; Monoterpenos di-hidroxilados e hidroxi-nitrogenados 1,2 e 1,3 como ligantes quirais em reacao de reformatsky assimetrica

    Energy Technology Data Exchange (ETDEWEB)

    Ribeiro, Carlos Magno R.; Morita, Cristina M.; Maia, Monica P. [Universidade Federal Fluminense (UFF), Niteroi, RJ (Brazil). Inst. de Quimica. Dept. de Quimica Organica]. E-mail: gqocmrr@vm.uff.br

    2008-07-01

    This study describes the use of three (-)-{alpha}-pinene derivatives, one diol-1,2 [(-)- (1R, 2R, 3S, 5R)-2,6,6-trimethylbicyclo[3.1.1]heptane-2,3-diol 4] and two pyridine-hydroxy derivatives [(+)-(1R,2S,3R,5S)-2,6,6- trimethyl-3-(2-pyridinylmethyl)bicyclo[3.1.1]heptane-3-ol 7 and (-)-(1R,2S,3R,5S)-2,6,6-trimethyl-3-[2-(2-pyridinyl) ethyl]bicyclo[3.1.1]heptane-3-ol 8]; one diol-1,3 [(-)-(1S,2R,5S)-2-(1-hydroxy-1-methylethyl)-5-methylcyclohexanol 5] derived from (+)-isopulegol 2 and one diol-1,3 [(+)-(1R,2R,5R)-2-(1-hydroxy-1-methylethyl)-5-methylcyclohexanol 6] derived from (+)-neoisopulegol 3, as ligands in the asymmetric Reformatsky reaction. The best enantiomeric excess of {beta}-hydroxy ester obtained in the Reformatsky asymmetric reaction was 18% using ligand 6, and the chemical yield of the reactions was 65% on average. (author)

  4. Asymmetrical international attitudes

    NARCIS (Netherlands)

    Van Oudenhoven, JP; Askevis-Leherpeux, F; Hannover, B; Jaarsma, R; Dardenne, B

    2002-01-01

    In general, attitudes towards nations have a fair amount of reciprocity: nations either like each other are relatively indifferent to each other or dislike each other Sometimes, however international attitudes are asymmetrical. In this study, we use social identity theory in order to explain asymmet

  5. Asymmetric catalysis with helical polymers

    NARCIS (Netherlands)

    Megens, Rik P.; Roelfes, Gerard

    Inspired by nature, the use of helical biopolymer catalysts has emerged over the last years as a new approach to asymmetric catalysis. In this Concept article the various approaches and designs and their application in asymmetric catalysis will be discussed.

  6. Asymmetric catalysis with helical polymers

    NARCIS (Netherlands)

    Megens, Rik P.; Roelfes, Gerard

    2011-01-01

    Inspired by nature, the use of helical biopolymer catalysts has emerged over the last years as a new approach to asymmetric catalysis. In this Concept article the various approaches and designs and their application in asymmetric catalysis will be discussed.

  7. Asymmetric extractions in orthodontics

    OpenAIRE

    Camilo Aquino Melgaço; Mônica Tirre de Souza Araújo

    2012-01-01

    INTRODUCTION: Extraction decisions are extremely important in during treatment planning. In addition to the extraction decision orthodontists have to choose what tooth should be extracted for the best solution of the problem and the esthetic/functional benefit of the patient. OBJECTIVE: This article aims at reviewing the literature relating the advantages, disadvantages and clinical implications of asymmetric extractions to orthodontics. METHODS: Keywords were selected in English and Portugue...

  8. Asymmetric information and economics

    Science.gov (United States)

    Frieden, B. Roy; Hawkins, Raymond J.

    2010-01-01

    We present an expression of the economic concept of asymmetric information with which it is possible to derive the dynamical laws of an economy. To illustrate the utility of this approach we show how the assumption of optimal information flow leads to a general class of investment strategies including the well-known Q theory of Tobin. Novel consequences of this formalism include a natural definition of market efficiency and an uncertainty principle relating capital stock and investment flow.

  9. Asymmetric Evolutionary Games.

    Directory of Open Access Journals (Sweden)

    Alex McAvoy

    2015-08-01

    Full Text Available Evolutionary game theory is a powerful framework for studying evolution in populations of interacting individuals. A common assumption in evolutionary game theory is that interactions are symmetric, which means that the players are distinguished by only their strategies. In nature, however, the microscopic interactions between players are nearly always asymmetric due to environmental effects, differing baseline characteristics, and other possible sources of heterogeneity. To model these phenomena, we introduce into evolutionary game theory two broad classes of asymmetric interactions: ecological and genotypic. Ecological asymmetry results from variation in the environments of the players, while genotypic asymmetry is a consequence of the players having differing baseline genotypes. We develop a theory of these forms of asymmetry for games in structured populations and use the classical social dilemmas, the Prisoner's Dilemma and the Snowdrift Game, for illustrations. Interestingly, asymmetric games reveal essential differences between models of genetic evolution based on reproduction and models of cultural evolution based on imitation that are not apparent in symmetric games.

  10. Asymmetric extractions in orthodontics

    Directory of Open Access Journals (Sweden)

    Camilo Aquino Melgaço

    2012-04-01

    Full Text Available INTRODUCTION: Extraction decisions are extremely important in during treatment planning. In addition to the extraction decision orthodontists have to choose what tooth should be extracted for the best solution of the problem and the esthetic/functional benefit of the patient. OBJECTIVE: This article aims at reviewing the literature relating the advantages, disadvantages and clinical implications of asymmetric extractions to orthodontics. METHODS: Keywords were selected in English and Portuguese and the EndNote 9 program was used for data base search in PubMed, Web of Science (WSc and LILACS. The selected articles were case reports, original articles and prospective or retrospective case-control studies concerning asymmetrical extractions of permanent teeth for the treatment of malocclusions. CONCLUSION: According to the literature reviewed asymmetric extractions can make some specific treatment mechanics easier. Cases finished with first permanent molars in Class II or III relationship in one or both sides seem not to cause esthetic or functional problems. However, diagnosis knowledge and mechanics control are essential for treatment success.

  11. Chiral N,N’-Dioxide-Ni(Ⅱ) Complex Catalyzed Asymmetric Carbonyl-Ene Reaction of Ethyl Trifluoropyruvate%手性氮氧-Ni(Ⅱ)络合物催化三氟甲基酮酸酯的不对称羰基ene反应

    Institute of Scientific and Technical Information of China (English)

    郑柯; 林丽丽; 冯小明

    2012-01-01

    本工作对手性氮氧–镍络合物催化剂在不对称羰基ene反应中的应用进行了深入研究,通过对配体结构和反应条件的优化,实现了三氟甲基酮酸酯的不对称羰基ene反应.实验发现,氮氧配体的结构对反应对映选择性有很大影响,其中酰胺结构中苯环2,6-位大位阻供电取代基对于反应立体选择性控制起着至关重要的作用.该催化体系有广泛的底物普适性,对一系列α-甲基烯烃都能得到高达80%~96%的收率和97%~〉99%ee的对映选择性.同时,通过对照实验以及对催化剂单晶结构的分析,提出了可能的反应过渡态,为该系列催化剂的拓展提供了基础.%The optically active homoallylic alcohols are widespread in natural products and have been frequently used as convenient building blocks in organic synthesis.As one of the most efficient synthetic methods to obtain chiral homoallylic alcohols,the asymmetric ene reaction of carbonyl compounds has attracted significant attentions.N,N’-dioxide-amide compounds,which could be easily prepared from chiral amino acids,have been developed into a type of privileged ligand and organocatalyst in various asymmetric reactions.On the other hand,the fluoroorganic compounds are important building blocks for the total synthesis of complex natural products,pharmaceuticals,and plant pesticides due to the unique abilities of the fluorine atom to significantly modify their physicochemical and biological properties.In recent years,the interest of the pharmaceutical industry in trifluoromethyl-containing compounds has grown significantly.In this manuscript,a series of Ni(II)-N,N’-dioxide complexes have been investigated for the asymmetric carbonyl-ene reaction of ethyl trifluoropyruvate.It was found that the electronic and steric characteristics of substituents on the amide moieties of the ligand greatly affected the reaction outcomes.The catalyst L4 with bulky and electron-donating groups at the

  12. Asymmetric synthesis v.4

    CERN Document Server

    Morrison, James

    1984-01-01

    Asymmetric Synthesis, Volume 4: The Chiral Carbon Pool and Chiral Sulfur, Nitrogen, Phosphorus, and Silicon Centers describes the practical methods of obtaining chiral fragments. Divided into five chapters, this book specifically examines initial chiral transmission and extension. The opening chapter describes the so-called chiral carbon pool, the readily available chiral carbon fragments used as building blocks in synthesis. This chapter also provides a list of 375 chiral building blocks, along with their commercial sources, approximate prices, and methods of synthesis. Schemes involving

  13. Asymmetric flow networks

    OpenAIRE

    Olaizola Ortega, María Norma; Valenciano Llovera, Federico

    2012-01-01

    This paper provides a new model of network formation that bridges the gap between the two benchmark models by Bala and Goyal, the one-way flow model, and the two-way flow model, and includes both as particular extreme cases. As in both benchmark models, in what we call an "asymmetric flow" network a link can be initiated unilaterally by any player with any other, and the flow through a link towards the player who supports it is perfect. Unlike those models, in the opposite direction there is ...

  14. De novo synthesis of natural products via the asymmetric hydration of polyenes.

    Science.gov (United States)

    Wang, Yanping; Xing, Yalan; Zhang, Qi; O'Doherty, George A

    2011-08-14

    For the last ten years our group has been working toward the development of an asymmetric hydration approach to polyketide natural products based on the regioselective hydration of di- and tri-enoates. Key to the success of this approach is the recognition that both high regiocontrol and asymmetric induction could be obtained by the use of a Sharpless asymmetric dihydroxylation reaction. Herein we describe the development of the method and its application to natural product total synthesis.

  15. Asymmetric Aminalization via Cation-Binding Catalysis

    DEFF Research Database (Denmark)

    Park, Sang Yeon; Liu, Yidong; Oh, Joong Suk

    2017-01-01

    Asymmetric cation-binding catalysis, in principle, can generate "chiral" anionic nucleophiles, where the counter cations are coordinated within chiral environments. Nitrogen-nucleophiles are intrinsically basic, therefore, its use as nucleophiles is often challenging and limiting the scope...... of the reaction. Particularly, a formation of configurationally labile aminal centers with alkyl substituents has been a formidable challenge due to the enamine/imine equilibrium of electrophilic substrates. Herein, we report enantioselective nucleophilic addition reactions of potassium phthalimides to Boc......-protected alkyl- and aryl-substituted α-amido sulfones. In-situ generated imines smoothly reacted with the nitrogen nucleophiles to corresponding aminals with good to excellent enantioselectivitiy under mild reaction conditions. In addition, transformation of aminal products gave biologically relevant...

  16. Highly selective synthesis of conjugated dienoic and trienoic esters via alkyne elementometalation-Pd-catalyzed cross-coupling.

    Science.gov (United States)

    Wang, Guangwei; Mohan, Swathi; Negishi, Ei-ichi

    2011-07-12

    All four stereoisomers (7-10) of ethyl undeca-2,4-dienoate were prepared in ≥ 98% isomeric purity by Pd-catalyzed alkenylation (Negishi coupling) using ethyl (E)- and (Z)-β-bromoacrylates. Although the stereoisomeric purity of the 2Z,4E-isomer (8) prepared by Suzuki coupling using conventional alkoxide and carbonate bases was ≤ 95%, as reported earlier, the use of CsF or (n)Bu(4)NF as a promoter base has now been found to give all of 7-10 in ≥ 98% selectivity. Other widely known methods reveal considerable limitations. Heck alkenylation was satisfactory for the syntheses of the 2E,4E and 2E,4Z isomers of ≥ 98% purity, but the purity of the 2Z,4E isomer was ≤ 95%. Mutually complementary Horner-Wadsworth-Emmons and Still-Gennari (SG) olefinations are also of considerably limited scopes. Neither 2E,4Z nor 2Z,4Z isomer is readily prepared in ≥ 90% selectivity. In addition to (2Z,4E)-dienoic esters, some (2Z,4E,6E)- and (2Z,4E,6Z)-trienoic esters have been prepared in ≥ 98% selectivity by a newly devised Pd-catalyzed alkenylation-SG olefination tandem process. As models for conjugated higher oligoenoic esters, all eight stereoisomers for ethyl trideca-2,4,6-trienoate (23-30) have been prepared in ≥ 98% overall selectivity.

  17. Asymmetric black dyonic holes

    Directory of Open Access Journals (Sweden)

    I. Cabrera-Munguia

    2015-04-01

    Full Text Available A 6-parametric asymptotically flat exact solution, describing a two-body system of asymmetric black dyons, is studied. The system consists of two unequal counterrotating Kerr–Newman black holes, endowed with electric and magnetic charges which are equal but opposite in sign, separated by a massless strut. The Smarr formula is generalized in order to take into account their contribution to the mass. The expressions for the horizon half-length parameters σ1 and σ2, as functions of the Komar parameters and of the coordinate distance, are displayed, and the thermodynamic properties of the two-body system are studied. Furthermore, the seven physical parameters satisfy a simple algebraic relation which can be understood as a dynamical scenario, in which the physical properties of one body are affected by the ones of the other body.

  18. The asymmetric sandwich theorem

    CERN Document Server

    Simons, Stephen

    2011-01-01

    We discuss the asymmetric sandwich theorem, a generalization of the Hahn-Banach theorem. As applications, we derive various results on the existence of linear functionals that include bivariate, trivariate and quadrivariate generalizations of the Fenchel duality theorem. Most of the results are about affine functions defined on convex subsets of vector spaces, rather than linear functions defined on vector spaces. We consider both results that use a simple boundedness hypothesis (as in Rockafellar's version of the Fenchel duality theorem) and also results that use Baire's theorem (as in the Robinson-Attouch-Brezis version of the Fenchel duality theorem). This paper also contains some new results about metrizable topological vector spaces that are not necessarily locally convex.

  19. Recent advances in cooperative bimetallic asymmetric catalysis: dinuclear Schiff base complexes.

    Science.gov (United States)

    Matsunaga, Shigeki; Shibasaki, Masakatsu

    2014-02-04

    Cooperative catalysis has proven to be a powerful strategy for realizing high reactivity and selectivity in asymmetric transformations. A variety of cooperative asymmetric catalysts have been developed over the last two decades. In this feature article, recent advances from our research on cooperative asymmetric catalysis, focusing on dinuclear Schiff base catalysis, are described. Design of dinuclear Schiff base catalysts and their applications in several asymmetric C-C and C-N bond-forming reactions under simple proton transfer conditions with perfect atom-economy are discussed in detail.

  20. Asymmetric photoredox transition-metal catalysis activated by visible light

    Science.gov (United States)

    Huo, Haohua; Shen, Xiaodong; Wang, Chuanyong; Zhang, Lilu; Röse, Philipp; Chen, Liang-An; Harms, Klaus; Marsch, Michael; Hilt, Gerhard; Meggers, Eric

    2014-11-01

    Asymmetric catalysis is seen as one of the most economical strategies to satisfy the growing demand for enantiomerically pure small molecules in the fine chemical and pharmaceutical industries. And visible light has been recognized as an environmentally friendly and sustainable form of energy for triggering chemical transformations and catalytic chemical processes. For these reasons, visible-light-driven catalytic asymmetric chemistry is a subject of enormous current interest. Photoredox catalysis provides the opportunity to generate highly reactive radical ion intermediates with often unusual or unconventional reactivities under surprisingly mild reaction conditions. In such systems, photoactivated sensitizers initiate a single electron transfer from (or to) a closed-shell organic molecule to produce radical cations or radical anions whose reactivities are then exploited for interesting or unusual chemical transformations. However, the high reactivity of photoexcited substrates, intermediate radical ions or radicals, and the low activation barriers for follow-up reactions provide significant hurdles for the development of efficient catalytic photochemical processes that work under stereochemical control and provide chiral molecules in an asymmetric fashion. Here we report a highly efficient asymmetric catalyst that uses visible light for the necessary molecular activation, thereby combining asymmetric catalysis and photocatalysis. We show that a chiral iridium complex can serve as a sensitizer for photoredox catalysis and at the same time provide very effective asymmetric induction for the enantioselective alkylation of 2-acyl imidazoles. This new asymmetric photoredox catalyst, in which the metal centre simultaneously serves as the exclusive source of chirality, the catalytically active Lewis acid centre, and the photoredox centre, offers new opportunities for the `green' synthesis of non-racemic chiral molecules.

  1. Asymmetric synthesis of (+)-hypusine.

    Science.gov (United States)

    Jain, R P; Albrecht, B K; DeMong, D E; Williams, R M

    2001-12-27

    Wittig reaction of (triphenylphosphoranylidene)acetonitrile with the lactone carbonyl of (5R,6S)-4-(benzyloxycarbonyl)-5,6-diphenyl-2,3,5,6-tetrahydro-4H-1,4-oxazin-2-one (3) and subsequent reduction generates morpholinylethylamine dihydrochloride (5) in quantitative yield and with excellent diastereoselectivity. Compound 5 was readily converted into hypusine dihydrochloride (1.2HCl) in overall 53% yield. [reaction: see text

  2. Recent Advances in the Application of Chiral Phosphine Ligands in Pd-Catalysed Asymmetric Allylic Alkylation

    Directory of Open Access Journals (Sweden)

    Erika Martin

    2011-01-01

    Full Text Available One of the most powerful approaches for the formation of simple and complex chiral molecules is the metal-catalysed asymmetric allylic alkylation. This reaction has been broadly studied with a great variety of substrates and nucleophiles under different reaction conditions and it has promoted the synthesis of new chiral ligands to be evaluated as asymmetric inductors. Although the mechanism as well as the active species equilibria are known, the performance of the catalytic system depends on the fine tuning of factors such as type of substrate, nucleophile nature, reaction medium, catalytic precursor and type of ligand used. Particularly interesting are chiral phosphines which have proved to be effective asymmetric inductors in several such reactions. The present review covers the application of phosphine-donor ligands in Pd-catalysed asymmetric allylic alkylation in the last decade.

  3. Asymmetric synthesis of propranolol, naftopidil and (R)-monobutyrin using a glycerol desymmetrization strategy

    National Research Council Canada - National Science Library

    Lokhande, Mahendra N; Chopade, Manojkumar U; Bhangare, Dattatrya N; Nikalje, Milind D

    2013-01-01

    .... The strategy for asymmetric synthesis of (R)/(S)-propranolol, (R)/(S)-naftopidil and (R)-monobutyrin with spiroketal formation by desymmetrization was employed and Mitsunobu reaction was used for epoxide and ether formation...

  4. Asymmetric Bessel modes.

    Science.gov (United States)

    Kotlyar, V V; Kovalev, A A; Soifer, V A

    2014-04-15

    We propose a new, three-parameter family of diffraction-free asymmetric elegant Bessel modes (aB-modes) with an integer and fractional orbital angular momentum (OAM). The aB-modes are described by the nth-order Bessel function of the first kind with complex argument. The asymmetry degree of the nonparaxial aB-mode is shown to depend on a real parameter c≥0: when c=0, the aB-mode is identical to a conventional radially symmetric Bessel mode; with increasing c, the aB-mode starts to acquire a crescent form, getting stretched along the vertical axis and shifted along the horizontal axis for c≫1. On the horizontal axis, the aB-modes have a denumerable number of isolated intensity zeros that generate optical vortices with a unit topological charge of opposite sign on opposite sides of 0. At different values of the parameter c, the intensity zeros change their location on the horizontal axis, thus changing the beam's OAM. An isolated intensity zero on the optical axis generates an optical vortex with topological charge n. The OAM per photon of an aB-mode depends near-linearly on c, being equal to ℏ(n+cI1(2c)/I0(2c)), where ℏ is the Planck constant and In(x) is a modified Bessel function.

  5. Asymmetric Gepner Models (Revisited)

    CERN Document Server

    Gato-Rivera, B

    2010-01-01

    We reconsider a class of heterotic string theories studied in 1989, based on tensor products of N=2 minimal models with asymmetric simple current invariants. We extend this analysis from (2,2) and (1,2) spectra to (0,2) spectra with SO(10) broken to the Standard Model. In the latter case the spectrum must contain fractionally charged particles. We find that in nearly all cases at least some of them are massless. However, we identify a large subclass where the fractional charges are at worst half-integer, and often vector-like. The number of families is very often reduced in comparison to the 1989 results, but there are no new tensor combinations yielding three families. All tensor combinations turn out to fall into two classes: those where the number of families is always divisible by three, and those where it is never divisible by three. We find an empirical rule to determine the class, which appears to extend beyond minimal N=2 tensor products. We observe that distributions of physical quantities such as th...

  6. Magnetically Modified Asymmetric Supercapacitors Project

    Data.gov (United States)

    National Aeronautics and Space Administration — This Small Business Innovation Research Phase I project is for the development of an asymmetric supercapacitor that will have improved energy density and cycle life....

  7. On Asymmetric Quantum MDS Codes

    CERN Document Server

    Ezerman, Martianus Frederic; Ling, San

    2010-01-01

    Assuming the validity of the MDS Conjecture, the weight distribution of all MDS codes is known. Using a recently-established characterization of asymmetric quantum error-correcting codes, linear MDS codes can be used to construct asymmetric quantum MDS codes with $d_{z} \\geq d_{x}\\geq 2$ for all possible values of length $n$ for which linear MDS codes over $\\F_{q}$ are known to exist.

  8. Asymmetric synthesis of (-)-adaline.

    Science.gov (United States)

    Itoh, Toshimasa; Yamazaki, Naoki; Kibayashi, Chihiro

    2002-07-25

    [reaction: see text] An enantioselective total synthesis of (-)-adaline has been achieved starting from a chiral 6,6-disubstituted piperidone derivative previously prepared by diastereoselective allylation of a chiral tricyclic N-acyl-N,O-acetal. The key steps include lithium ion-activated SN2-type alkynylation of the tricyclic N,O-acetal leading to exclusive formation of the (6S)-ethynylpiperidine and ring-closing olefin metathesis of the (2R,6S)-cis-2,6-dialkenylpiperidine for constructing the bridged azabicyclononane.

  9. Asymmetric 1,8/13,2,x-M2C2B10 14-vertex metallacarboranes by direct electrophilic insertion reactions; the VCD and BHD methods in critical analysis of cage C atom positions.

    Science.gov (United States)

    McAnaw, Amelia; Lopez, Maria Elena; Ellis, David; Rosair, Georgina M; Welch, Alan J

    2014-04-07

    The isolation of six isomeric, low-symmetry, dicobaltacarboranes with bicapped hexagonal antiprismatic cage structures, always in low yield, is described from reactions in which 13-vertex cobaltacarborane anions and sources of cobalt-containing cations were present. The vertex-to-centroid distance (VCD) and boron-H distance (BHD) methods are used to locate the correct C atom positions in the cages, thus allowing the compounds to be identified as 1,13-Cp2-1,13,2,10-closo-Co2C2B10H12 (1), 1,8-Cp2-3-OEt-1,8,2,10-closo-Co2C2B10H11 (2), 1,13-Cp2-1,13,2,9-closo-Co2C2B10H12 (3), 1,8-Cp2-1,8,2,4-closo-Co2C2B10H12 (4), 1,13-Cp2-1,13,2,4-closo-Co2C2B10H12 (5) and 1,8-Cp2-1,8,2,5-closo-Co2C2B10H12 (6). It is shown that a common alternative method of cage C atom identification, using refined (as B) U(eq) values, does not work well, at least in these cases. Having identified the correct isomeric forms of the six dicobaltacarboranes, their syntheses are tentatively rationalised in terms of the direct electrophilic insertion of a {CpCo(+)} fragment into [CpCoC2B10](-) anions and it is demonstrated that compounds 1, 4, 5 and 6 can be successfully prepared by deliberately performing such reactions.

  10. Asymmetric distances for binary embeddings.

    Science.gov (United States)

    Gordo, Albert; Perronnin, Florent; Gong, Yunchao; Lazebnik, Svetlana

    2014-01-01

    In large-scale query-by-example retrieval, embedding image signatures in a binary space offers two benefits: data compression and search efficiency. While most embedding algorithms binarize both query and database signatures, it has been noted that this is not strictly a requirement. Indeed, asymmetric schemes that binarize the database signatures but not the query still enjoy the same two benefits but may provide superior accuracy. In this work, we propose two general asymmetric distances that are applicable to a wide variety of embedding techniques including locality sensitive hashing (LSH), locality sensitive binary codes (LSBC), spectral hashing (SH), PCA embedding (PCAE), PCAE with random rotations (PCAE-RR), and PCAE with iterative quantization (PCAE-ITQ). We experiment on four public benchmarks containing up to 1M images and show that the proposed asymmetric distances consistently lead to large improvements over the symmetric Hamming distance for all binary embedding techniques.

  11. Does asymmetric correlation affect portfolio optimization?

    Science.gov (United States)

    Fryd, Lukas

    2017-07-01

    The classical portfolio optimization problem does not assume asymmetric behavior of relationship among asset returns. The existence of asymmetric response in correlation on the bad news could be important information in portfolio optimization. The paper applies Dynamic conditional correlation model (DCC) and his asymmetric version (ADCC) to propose asymmetric behavior of conditional correlation. We analyse asymmetric correlation among S&P index, bonds index and spot gold price before mortgage crisis in 2008. We evaluate forecast ability of the models during and after mortgage crisis and demonstrate the impact of asymmetric correlation on the reduction of portfolio variance.

  12. Asymmetric Synthesis via Chiral Aziridines

    DEFF Research Database (Denmark)

    Tanner, David Ackland; Harden, Adrian; Wyatt, Paul

    1996-01-01

    A series of chiral bis(aziridines) has been synthesised and evaluated as chelating ligands for a variety of asymmetric transformations mediated by metals [Os (dihydroxylation), Pd (allylic alkylation) Cu (cyclopropanation and aziridination, Li (1,2-addition of organolithiums to imines)]. In the b......A series of chiral bis(aziridines) has been synthesised and evaluated as chelating ligands for a variety of asymmetric transformations mediated by metals [Os (dihydroxylation), Pd (allylic alkylation) Cu (cyclopropanation and aziridination, Li (1,2-addition of organolithiums to imines...

  13. Ideal 3D asymmetric concentrator

    Energy Technology Data Exchange (ETDEWEB)

    Garcia-Botella, Angel [Departamento Fisica Aplicada a los Recursos Naturales, Universidad Politecnica de Madrid, E.T.S.I. de Montes, Ciudad Universitaria s/n, 28040 Madrid (Spain); Fernandez-Balbuena, Antonio Alvarez; Vazquez, Daniel; Bernabeu, Eusebio [Departamento de Optica, Universidad Complutense de Madrid, Fac. CC. Fisicas, Ciudad Universitaria s/n, 28040 Madrid (Spain)

    2009-01-15

    Nonimaging optics is a field devoted to the design of optical components for applications such as solar concentration or illumination. In this field, many different techniques have been used for producing reflective and refractive optical devices, including reverse engineering techniques. In this paper we apply photometric field theory and elliptic ray bundles method to study 3D asymmetric - without rotational or translational symmetry - concentrators, which can be useful components for nontracking solar applications. We study the one-sheet hyperbolic concentrator and we demonstrate its behaviour as ideal 3D asymmetric concentrator. (author)

  14. DFT Study on the Bifunctional Ionic Liquid [Promim]^+ [CF3CO2]^--Supported Asymmetric Aldol Reaction%双官能团离子液体[Promim]^+[CF3CO2]^-支撑不对称Aldol反应的密度泛函理论研究

    Institute of Scientific and Technical Information of China (English)

    张金生; 陈卓; 谢辉; 申婧; 许亮

    2011-01-01

    By using the B3LYP method of the density functional theory(DFT),the bifunctional ionic liquid(IL) [Promim]+ [CF3CO2]--supported asymmetric aldol reaction between ketone and o-nitrobenzaldehyde is theoretically studied.The results demonstrate that bifunctional proline and imidazole fragments of the IL coordinate to catalyze the reactions.The overall reactions are initiated by a nucleophilic addition reaction of the proline fragment with the carbonyl group of ketone,and subsequently go through a dehydration reaction,a dehydrogenation,a nucleophilic addition of enamine with aldehyde,a hydration reaction and a regeneration of the catalyst.The first step is rate-controlling,and the chiral carbon center is generated in the enamine nucleophilic addition with the aldehyde.It is a new finding that the 2-position hydrogen of the imidazole fragment takes part in the dehydration reaction leading to an imine onium IM1-2.Moreover,a water molecule acts as a hydrogen shuttle to transport a hydrogen atom from methyl of ketone to carbonyl-oxygen of aldehyde fragment.The electron-withdrawing inductive effect of ortho-nitro-group in phenyl decreases the electron density of the carbonyl carbon and increases its electrophilic ability,thus promoting the nucleophilic addition reaction of the enamine with aldehyde.On the whole,the ionic liquid of [Promim]+ [CF3CO2]- decreases the reaction barriers excluding the last steps.%用密度泛函理论B3LYP方法对双官能团离子液体[Promim]+[CF3CO2]-支撑丙酮与邻-硝基苯甲醛不对称aldol反应进行了研究.结果表明,该离子液体的脯胺酸和咪唑基团一起对反应产生催化作用.整个反应包括:丙酮的羰基与脯胺酸基团的胺基间的亲核加成反应,咪唑2-位氢参与的脱水反应生成亚胺IM1-2,丙酮甲基脱氢反应生成烯胺I M1-3,苯甲醛与烯胺的亲核加成反应,水加成反应和催化剂再生反应.第一步骤是速率控制步骤,产物羟基位碳原子的

  15. Highly Enantioselective Organocatalytic Asymmetric Mukaiyama-aldol Reaction of Difluoroenoxysilanes with β,γ-Unsaturated α-Ketoesters%高对映选择性的有机催化的二氟烯醇硅醚与β,γ-不饱和-α-酮酸酯的不对称Mukaiyama-aldol反应

    Institute of Scientific and Technical Information of China (English)

    刘运林; 周剑

    2012-01-01

    We report the first example of catalytic asymmetric reaction of difluoroenoxysilanes 1 and β,γ-unsaturated α-ketoesters 2. In the presence of tertiary amine or tertiary amine-H-bonding donor bifunctional catalysts, it was found that the reaction selectively took place at the ketone moiety of ketoesters 2, and no conjugate reaction happened. Hydronquinine derived urea catalyst 11 was identified as a powerful catalyst for this Mukaiyama-aldol reaction to finnish a-difluoroalkyl substituted tertiary alcohols in good to high yield (44%-81%), with moderate to excellent enantioselectivity (72%-96%). The optimum reaction condition was determined to run the reaction at -40 ℃ using THF as the solvent, in the presence of 10 mol% of chiral catalyst 11. The reaction possibly proceeded via the dual activation of both reaction partners: the tertiary amine moiety of catalyst 11 working as a Lewis base to activate difluoroenoxysilanes 1, while the urea part of the catalyst as a Bronsted acid to activate carbonyl group of ketoesters 2. Different aryl substituted difluoroenoxysilanes 1 and ),-aryl substi- tuted β,γ-unsaturated a-ketoesters 2 all worked well under the established reaction condition, with 15 examples provided. The thus obtained chiral α-difluoroalkyl substituted tertiary alcohols were not only valuable in the medicinal research, but also versatile building blocks for the synthesis of a variety of difluoroalkyl-substituted chiral compounds. For example, the selec- tive reduction of the ketone or ester group of product 3g has been realized by using NaBH4 or Et3SiH as the reducing agents, giving the triol 14 or diol 15 in moderate yield without the loss ofee.%首次研究了二氟烯醇硅醚1与β,γ-不饱和酮酸酯2的反应.发现不论使用叔胺或叔胺-氢键给体双功能催化剂,均专一地发生Mukaiyama-aldol反应生成相应的叔醇3.利用手性氢化奎宁衍生的双功能脲催化剂11高对映选择性地实现了这一反

  16. Activation of carboxylic acids in asymmetric organocatalysis.

    Science.gov (United States)

    Monaco, Mattia Riccardo; Poladura, Belén; Diaz de Los Bernardos, Miriam; Leutzsch, Markus; Goddard, Richard; List, Benjamin

    2014-07-01

    Organocatalysis, catalysis using small organic molecules, has recently evolved into a general approach for asymmetric synthesis, complementing both metal catalysis and biocatalysis. Its success relies to a large extent upon the introduction of novel and generic activation modes. Remarkably though, while carboxylic acids have been used as catalyst directing groups in supramolecular transition-metal catalysis, a general and well-defined activation mode for this useful and abundant substance class is still lacking. Herein we propose the heterodimeric association of carboxylic acids with chiral phosphoric acid catalysts as a new activation principle for organocatalysis. This self-assembly increases both the acidity of the phosphoric acid catalyst and the reactivity of the carboxylic acid. To illustrate this principle, we apply our concept in a general and highly enantioselective catalytic aziridine-opening reaction with carboxylic acids as nucleophiles.

  17. Reaction Characteristics of Asymmetric Synthesis of (2S,5S)-2,5-Hexanediol Catalyzed with Baker's Yeast Number 6%面包酵母No.6催化不对称合成(2S,5S)-2,5-已二醇反应特性

    Institute of Scientific and Technical Information of China (English)

    肖美添; 叶静; 张亚武; 黄雅燕

    2009-01-01

    Baker's yeast number 6 was selected by screening. It showed good catalytic activity and enantioselec-tivity for asymmetric reduction of 2,5-hexancdione to produce (2S,5S)-2,5-hexanediol. Gas chromatography-mass spectrometry (GC-MS) revealed that the intermediate was (S)-5-hydroxyhexane-2-one. Reduction of 2,5-hexanedione proceeded in a two-step reaction. The hydroxyketone was initially formed, and this intermediate was further re-duced to the diol. Factors influencing the product yield and the enantiomeric excess of the reduction of 2,5-hexandione catalyzed by baker's yeast number 6 were investigated. Higher concentration (≤100 mmol·L-1) of 2,5-hexandione did not influence 5-hydroxyhexane-2-one production, but 2,5-hexanediol production was inhibited by excess accumulation (>30 mmol·L-1) of intermediate. The optimal conditions were glucose as the co-substrate at an initial glucose concentration of 20 g·L-1, 34℃, pH 7.0 and cell concentration 60 g-L"1 (cell dry mass). Under the optimal condition and an initial substrate concentration of 30 mmol·L-1, the yield of 2,5-hexandiol was 78.7% and the enantiomeric excess of (2S,5S)-2,5-hexandiol was 94.4% for 24-h reduction.

  18. Chiral cyclopentadienylruthenium sulfoxide catalysts for asymmetric redox bicycloisomerization

    Science.gov (United States)

    Ryan, Michael C; Rao, Meera

    2016-01-01

    Summary A full account of our efforts toward an asymmetric redox bicycloisomerization reaction is presented in this article. Cyclopentadienylruthenium (CpRu) complexes containing tethered chiral sulfoxides were synthesized via an oxidative [3 + 2] cycloaddition reaction between an alkyne and an allylruthenium complex. Sulfoxide complex 1 containing a p-anisole moiety on its sulfoxide proved to be the most efficient and selective catalyst for the asymmetric redox bicycloisomerization of 1,6- and 1,7-enynes. This complex was used to synthesize a broad array of [3.1.0] and [4.1.0] bicycles. Sulfonamide- and phosphoramidate-containing products could be deprotected under reducing conditions. Catalysis performed with enantiomerically enriched propargyl alcohols revealed a matched/mismatched effect that was strongly dependent on the nature of the solvent. PMID:27559366

  19. Asymmetric trienamine catalysis: new opportunities in amine catalysis.

    Science.gov (United States)

    Kumar, Indresh; Ramaraju, Panduga; Mir, Nisar A

    2013-02-07

    Amine catalysis, through HOMO-activating enamine and LUMO-activating iminium-ion formation, is receiving increasing attention among other organocatalytic strategies, for the activation of unmodified carbonyl compounds. Particularly, the HOMO-raising activation concept has been applied to the greatest number of asymmetric transformations through enamine, dienamine, and SOMO-activation strategies. Recently, trienamine catalysis, an extension of amine catalysis, has emerged as a powerful tool for synthetic chemists with a novel activation strategy for polyenals/polyenones. In this review article, we discuss the initial developments of trienamine catalysis for highly asymmetric Diels-Alder reactions with different dienophiles and emerging opportunities for other types of cycloadditions and cascade reactions.

  20. Development of chiral sulfoxide ligands for asymmetric catalysis.

    Science.gov (United States)

    Trost, Barry M; Rao, Meera

    2015-04-20

    Nitrogen-, phosphorus-, and oxygen-based ligands with chiral backbones have been the historic workhorses of asymmetric transition-metal-catalyzed reactions. On the contrary, sulfoxides containing chirality at the sulfur atom have mainly been used as chiral auxiliaries for diastereoselective reactions. Despite several distinct advantages over traditional ligand scaffolds, such as the proximity of the chiral information to the metal center and the ability to switch between S and O coordination, these compounds have only recently emerged as a versatile class of chiral ligands. In this Review, we detail the history of the development of chiral sulfoxide ligands for asymmetric catalysis. We also provide brief descriptions of metal-sulfoxide bonding and strategies for the synthesis of enantiopure sulfoxides. Finally, insights into the future development of this underutilized ligand class are discussed.

  1. Chiral cyclopentadienylruthenium sulfoxide catalysts for asymmetric redox bicycloisomerization

    Directory of Open Access Journals (Sweden)

    Barry M. Trost

    2016-06-01

    Full Text Available A full account of our efforts toward an asymmetric redox bicycloisomerization reaction is presented in this article. Cyclopentadienylruthenium (CpRu complexes containing tethered chiral sulfoxides were synthesized via an oxidative [3 + 2] cycloaddition reaction between an alkyne and an allylruthenium complex. Sulfoxide complex 1 containing a p-anisole moiety on its sulfoxide proved to be the most efficient and selective catalyst for the asymmetric redox bicycloisomerization of 1,6- and 1,7-enynes. This complex was used to synthesize a broad array of [3.1.0] and [4.1.0] bicycles. Sulfonamide- and phosphoramidate-containing products could be deprotected under reducing conditions. Catalysis performed with enantiomerically enriched propargyl alcohols revealed a matched/mismatched effect that was strongly dependent on the nature of the solvent.

  2. DIFLUORPHOS and SYNPHOS in asymmetric catalysis: Synthetic applications

    Indian Academy of Sciences (India)

    Sebastien Prevost; Tahar Ayad; Jean-Pierre Genet; Phannarath Phansavath; Virginie Ratovelomanana-Vidal

    2014-03-01

    Enantiomerically pure diphosphines play an important role in various homogeneous metalcatalyzed asymmetric reactions. Over the last few years, our group has been involved in the design and synthesis of atropisomeric ligands named SYNPHOS and DIFLUORPHOS with complementary stereoelectronic properties. This paper shows the high catalytic performances of DIFLUORPHOS, SYNPHOS and SYNPHOS analogues for some C-H and C-C bond forming processes as well as for the synthesis of biorelevant targets.

  3. Metal and organo-catalysed asymmetric hydroaminomethylation of styrenes

    Institute of Scientific and Technical Information of China (English)

    Barbara Villa-Marcos; Jianliang Xiao

    2015-01-01

    A new protocol that enables asymmetric hydroaminomethylation of styrenes to afford chiral amines has been developed. Catalysed by an Rh‐phosphine species and a chiral phosphoric acid, styrenes are converted intoβ‐chiral amines with good enantioselectivities under syngas in the presence of an amine and Hantzsch ester. The reaction involves two key steps, hydroformylation and reductive amination, with the former catalysed by the Rh species whilst the latter by the phosphoric acid.

  4. Synthesis of Asymmetric Propanetriol Analogues

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    From natural tartaric acid, (R)-2-benzyloxy-3-(2-tetrahydropyranyloxy) propanol 3 was designed and synthesized, and (R)-2-benzyloxy-3-(4-methoxybenzyloxy) propanol 7 was prepared in a new method. They can be used as chiral synthons of lysophosphatidic acid and other compounds with asymmetric propanetriol backbone.

  5. Catalytic Asymmetric Bromocyclization of Polyenes.

    Science.gov (United States)

    Samanta, Ramesh C; Yamamoto, Hisashi

    2017-02-01

    The first catalytic asymmetric bromonium ion-induced polyene cyclization has been achieved by using a chiral BINOL-derived thiophosphoramide catalyst and 1,3-dibromo-5,5-dimethylhydantoin as an electrophilic bromine source. Bromocyclization products are obtained in high yields, with good enantiomeric ratios and high diastereoselectivity, and are abundantly found as scaffolds in natural products.

  6. Asymmetric cyanation of imines via dipeptide-derived organophosphine dual-reagent catalysis

    Science.gov (United States)

    Wang, Hong-Yu; Zheng, Chang-Wu; Chai, Zhuo; Zhang, Jia-Xing; Zhao, Gang

    2016-09-01

    Over the past few decades, enantioselective phosphine organocatalysis has evolved rapidly into a highly efficient catalytic strategy for a range of useful reactions. However, as restricted by the traditional catalytic modes, some important reactions, such as asymmetric Strecker-type reactions, have thus far been out of reach of this strategy. Reported herein is an application of enantioselective phosphine organocatalysis for asymmetric Strecker-type reactions, enabled by a dual-reagent catalyst system in which the key organophosphorus zwitterion intermediate, generated in situ by mixing a chiral dipeptide-derived multifunctional organophosphine with methyl acrylate, is used as a highly efficient chiral Lewis base catalyst. The high efficiency of this catalytic system is demonstrated in the asymmetric cyanation of isatin-derived ketimines and azomethine aldimines as well as in the kinetic resolution of racemic 3-substituted azomethines. Mechanistic studies provide experimental evidence for the intermediacy of the putative zwitterion and its role as a catalytically active Lewis base.

  7. Selfhealing of asymmetric Bessel-like modes

    DEFF Research Database (Denmark)

    Israelsen, Stine Møller; Rishøj, Lars Søgaard; Rottwitt, Karsten

    2014-01-01

    We numerically investigate asymmetric Bessel-like modes in an aircladding fiber. The selfhealing ability of asymmetric Bessel-like modes is demonstrated and quantified including the angular dependency of this ability.......We numerically investigate asymmetric Bessel-like modes in an aircladding fiber. The selfhealing ability of asymmetric Bessel-like modes is demonstrated and quantified including the angular dependency of this ability....

  8. Rhodium-catalyzed asymmetric ring opening of azabenzonorbornadiene with substituted piperazine nucleophiles

    Institute of Scientific and Technical Information of China (English)

    Lei Xie; Ding Qiao Yang; Shuang Qi Zhao; Huan Wang; Li Hua Liang; Ren Shi Luo

    2007-01-01

    We have developed an asymmetric ring opening reaction of azabenzonorbornadiene with substituted piperazine. By increasing the amount of catalyst (from 2.5 to 5%) and ligands (5 to 10%) as well as addition of ammonium iodide, the products can be obtained in high yield and the reaction time shortened dramatically, but the ee values were rather low.

  9. APPLICATION OF S-(+)-3-HYDROXYTETRAHYDROFURAN IN ASYMMETRIC-SYNTHESIS OF S-(+)-ATROLACTIC ACID

    NARCIS (Netherlands)

    TANDON, VK; AGARWAL, [No Value; van Leusen, A.M.

    1994-01-01

    S-(+)-3-Hydroxytetrahydrofuran (1) on reaction with phenylglyoxallyl chloride (2) forms S-(+)-3-tetrahydrofuranyl benzoyformate (3) in 88% yield. Further reaction of the alpha-ketoester 3 with MeLi at - 95 degrees C followed by basic hydrolysis results in asymmetric synthesis of S-(+)-atrolactic aci

  10. Asymmetric synthesis of pedamide using I2-induced heterocyclization to construct the skeleton

    Institute of Scientific and Technical Information of China (English)

    De Gang Liu; Ji Jun Xue; Zhi Xiang Xie; Li Ping Wei; Hua Bing Zhang; Ying Li

    2009-01-01

    An alternative approach to synthesize pedamide, a key building block of pederin was described. Iodine-induced asymmetric heterocyclization was used as the key step to construct the skeleton, a tetrahydropyran ring with three chiral centers. Brown's asymmetric allylation and Lewis acid-mediated allylation were investigated to introduce chains and chiral alcohols. Sharpless dihydroxylation decorated the side chain. And high optically pure target was obtained by removing the epimers formed in these reactions on column chromatography.

  11. P-chiral phosphine-sulfonate/palladium-catalyzed asymmetric copolymerization of vinyl acetate with carbon monoxide.

    Science.gov (United States)

    Nakamura, Akifumi; Kageyama, Takeharu; Goto, Hiroki; Carrow, Brad P; Ito, Shingo; Nozaki, Kyoko

    2012-08-01

    Utilization of palladium catalysts bearing a P-chiral phosphine-sulfonate ligand enabled asymmetric copolymerization of vinyl acetate with carbon monoxide. The obtained γ-polyketones have head-to-tail and isotactic polymer structures. The origin of the regio- and stereoregularities was elucidated by stoichiometric reactions of acylpalladium complexes with vinyl acetate. The present report for the first time demonstrates successful asymmetric coordination-insertion (co)polymerization of vinyl acetate.

  12. Recent developments in the catalytic asymmetric synthesis of alpha- and beta-amino acids.

    Science.gov (United States)

    Ma, Jun-An

    2003-09-22

    The stereoselective synthesis of amino acids is of great importance for the construction of optically active natural products and pharmaceuticals. Apart from enzymes, a broad repertoire of chiral reagents, auxiliaries, and catalysts can be used for the formation of amino acids. Asymmetric reactions using catalytic amounts of chiral molecules provide efficient methods for the generation of optically active proteinogenic and nonproteinogenic amino acids. This minireview collects recent work on catalytic asymmetric synthesis of alpha- and beta-amino acids.

  13. Updating the asymmetric osmium-catalyzed dihydroxylation (AD) mnemonic. Q2MM modeling and new kinetic measurements

    DEFF Research Database (Denmark)

    Fristrup, Peter; Tanner, David Ackland; Norrby, Per-Ola

    2003-01-01

    The mnemonic device for predicting stereoselectivities in the Sharpless asymmetric dihydroxylation (AD) reaction has been updated based on extensive computational studies. Kinetic measurements from competition reactions validate the new proposal. The interactions responsible for the high stereose......The mnemonic device for predicting stereoselectivities in the Sharpless asymmetric dihydroxylation (AD) reaction has been updated based on extensive computational studies. Kinetic measurements from competition reactions validate the new proposal. The interactions responsible for the high...... stereoselectivity in the title reaction are analyzed in detail and mapped onto the mnemonic device....

  14. Asymmetric Synthesis of Substituted Thiolanes through Domino Thia-Michael-Henry Dynamic Covalent Systemic Resolution using Lipase Catalysis.

    Science.gov (United States)

    Zhang, Yan; Vongvilai, Pornrapee; Sakulsombat, Morakot; Fischer, Andreas; Ramström, Olof

    2014-03-24

    Dynamic systems based on consecutive thia-Michael and Henry reactions were generated and transformed using lipase-catalyzed asymmetric transformation. Substituted thiolane structures with three contiguous stereocenters were resolved in the process in high yields and high enantiomeric excesses.

  15. Asymmetric Multilevel Diversity Coding and Asymmetric Gaussian Multiple Descriptions

    CERN Document Server

    Mohajer, Soheil; Diggavi, Suhas N

    2009-01-01

    We consider the asymmetric multilevel diversity (A-MLD) coding problem, where a set of $2^K-1$ information sources, ordered in a decreasing level of importance, is encoded into $K$ messages (or descriptions). There are $2^K-1$ decoders, each of which has access to a non-empty subset of the encoded messages. Each decoder is required to reproduce the information sources up to a certain importance level depending on the combination of descriptions available to it. We obtain a single letter characterization of the achievable rate region for the 3-description problem. In contrast to symmetric multilevel diversity coding, source-separation coding is not sufficient in the asymmetric case, and ideas akin to network coding need to be used strategically. Based on the intuitions gained in treating the A-MLD problem, we derive inner and outer bounds for the rate region of the asymmetric Gaussian multiple description (MD) problem with three descriptions. Both the inner and outer bounds have a similar geometric structure t...

  16. Asymmetric responses of international stock markets to trading volume

    Science.gov (United States)

    Gerlach, Richard; Chen, Cathy W. S.; Lin, Doris S. Y.; Huang, Ming-Hsiang

    2006-02-01

    The major goal of this paper is to examine the hypothesis that stock returns and return volatility are asymmetric, threshold nonlinear, functions of change in trading volume. A minor goal is to examine whether return spillover effects also display such asymmetry. Employing a double-threshold GARCH model with trading volume as a threshold variable, we find strong evidence supporting this hypothesis in five international market return series. Asymmetric causality tests lend further support to our trading volume threshold model and conclusions. Specifically, an increase in volume is positively associated, while decreasing volume is negatively associated, with the major price index in four of the five markets. The volatility of each series also displays an asymmetric reaction, four of the markets display higher volatility following increases in trading volume. Using posterior odds ratio, the proposed threshold model is strongly favored in three of the five markets, compared to a US news double threshold GARCH model and a symmetric GARCH model. We also find significant nonlinear asymmetric return spillover effects from the US market.

  17. Modelling asymmetric growth in crowded plant communities

    DEFF Research Database (Denmark)

    Damgaard, Christian

    2010-01-01

    A class of models that may be used to quantify the effect of size-asymmetric competition in crowded plant communities by estimating a community specific degree of size-asymmetric growth for each species in the community is suggested. The model consists of two parts: an individual size-asymmetric ......A class of models that may be used to quantify the effect of size-asymmetric competition in crowded plant communities by estimating a community specific degree of size-asymmetric growth for each species in the community is suggested. The model consists of two parts: an individual size...

  18. Terahertz metamaterial with asymmetric transmission

    CERN Document Server

    Singh, R; Menzel, C; Rockstuhl, C; Azad, A K; Cheville, R A; Lederer, F; Zhang, W; Zheludev, N I

    2009-01-01

    We show for the first time that a planar metamaterial, an array of coupled metal split-ring resonators with a unit cell lacking mirror symmetry, exhibits asymmetric transmission of terahertz radiation propagating through it in opposite directions. This intriguing effect, that is compatible with Lorentz reciprocity and time-reversal, depends on a directional difference in conversion efficiency of the incident circularly polarized wave into one of opposite handedness, that is only possible in lossy low-symmetry planar chiral metamaterials. We show that asymmetric transmission is linked to excitation of enantiomerically sensitive plasmons, these are induced charge-field excitations that depend on the mutual handedness of incident wave and metamaterial pattern. Various bands of positive, negative and zero phase and group velocities have been identified indicating the opportunity to develop polarization sensitive negative index and slow light media based on such metamaterials.

  19. Superpositions of asymmetrical Bessel beams.

    Science.gov (United States)

    Kotlyar, V V; Kovalev, A A; Soifer, V A

    2015-06-01

    We considered nonparaxial asymmetrical Bessel modes of the first and second types, which differ from a conventional symmetrical Bessel mode by a real-valued shift along one Cartesian coordinate and an imaginary shift along another (both shifts are equal in modulus). The first- and second-type Bessel modes differ only in signs of the shift and, therefore, have different orbital angular momentum (OAM) (integer or fractional). Addition and subtraction of complex amplitudes of two identical asymmetrical Bessel modes of the first and second type lead to light beams with the same integer OAM equal to the topological charge n of the original mode, but with different transverse intensity distributions, which depend on the shift magnitude. This proposed method allows controlling of the OAM of the beam with simultaneous changing of its shape, i.e., for matching with the object being trapped.

  20. Asymmetric information and macroeconomic dynamics

    Science.gov (United States)

    Hawkins, Raymond J.; Aoki, Masanao; Roy Frieden, B.

    2010-09-01

    We show how macroeconomic dynamics can be derived from asymmetric information. As an illustration of the utility of this approach we derive the equilibrium density, non-equilibrium densities and the equation of motion for the response to a demand shock for productivity in a simple economy. Novel consequences of this approach include a natural incorporation of time dependence into macroeconomics and a common information-theoretic basis for economics and other fields seeking to link micro-dynamics and macro-observables.

  1. Asymmetrical Γ-Source Inverters

    DEFF Research Database (Denmark)

    Wei, Mo; Poh Chiang, Loh; Blaabjerg, Frede

    2014-01-01

    , inverters with coupled transformers have been introduced, but they usually lead to high turns ratio, and hence many winding turns, at high gain. An alternative would then be the asymmetrical Γ-source inverters proposed in this paper, whose gain is raised by lowering their turns ratio toward unity. The input...... current drawn by the proposed inverters is smoother and, hence, more adaptable by the source. Theories and experimental results have been presented in this paper for validating the concepts proposed....

  2. Up-down asymmetric tokamaks

    CERN Document Server

    Ball, Justin

    2016-01-01

    Bulk toroidal rotation has proven capable of stabilising both dangerous MHD modes and turbulence. In this thesis, we explore a method to drive rotation in large tokamaks: up-down asymmetry in the magnetic equilibrium. We seek to maximise this rotation by finding optimal up-down asymmetric flux surface shapes. First, we use the ideal MHD model to show that low order external shaping (e.g. elongation) is best for creating up-down asymmetric flux surfaces throughout the device. Then, we calculate realistic up-down asymmetric equilibria for input into nonlinear gyrokinetic turbulence analysis. Analytic gyrokinetics shows that, in the limit of fast shaping effects, a poloidal tilt of the flux surface shaping has little effect on turbulent transport. Since up-down symmetric surfaces do not transport momentum, this invariance to tilt implies that devices with mirror symmetry about any line in the poloidal plane will drive minimal rotation. Accordingly, further analytic investigation suggests that non-mirror symmetri...

  3. Tourist Demand Reactions : Symmetric or Asymmetric across the Business Cycle?

    NARCIS (Netherlands)

    Bronner, Fred; de Hoog, Robert

    2017-01-01

    Economizing and spending priorities on different types of vacations are investigated during two periods: an economic downturn and returning prosperity. Two nation-wide samples of vacationers are used: one during a downturn, the other one at the start of the recovery period. Through comparing the

  4. Palladium-catalyzed asymmetric allylic substitution of 2-arylcyclohexenol derivatives: asymmetric total syntheses of (+)-crinamine, (-)-haemanthidine, and (+)-pretazettine.

    Science.gov (United States)

    Nishimata, Toyoki; Sato, Yoshihiro; Mori, Miwako

    2004-03-19

    Much interest has been shown in Amaryllidaceae alkaloids as synthetic targets due to their wide range of biological activities. Over 100 alkaloids have been isolated from members of the Amaryllidaceae family; most of them can be classified into eight skeletally homogeneous groups. We have succeeded in the first asymmetric total syntheses of the crinane-type alkaloids (+)-crinamine (1), (-)-haemanthidine (2), and (+)-pretazettine (3). The starting cyclohexenylamine 14 was obtained from allyl phosphonate 11c by palladium-catalyzed asymmetric amination in 82% yield and with 74% ee. The product was recrystallized from MeOH. Interestingly, (-)-14 with 99% ee was obtained from the mother liquor (74% recovery). Intramolecular carbonyl-ene reaction of (-)-10 proceeds in a highly stereoselective manner to give hexahydroindole derivative 9 as the sole product. In the Lewis-acid-catalyzed carbonyl-ene reaction, an interesting rearrangement product, 20, was isolated in high yield. From 9, (+)-crinamine was synthesized. Thus, the asymmetric total synthesis of (+)-crinamine was achieved in 10 steps from 11c, and the overall yield is 19%. The total synthesis of (-)-haemanthidine was also achieved from 9 by a short sequence of steps.

  5. Asymmetric Schiff bases derived from diaminomaleonitrile and their metal complexes

    Science.gov (United States)

    Yang, Jianjie; Shi, Rufei; Zhou, Pei; Qiu, Qiming; Li, Hui

    2016-02-01

    Asymmetric Schiff bases, due to its asymmetric structure, can be used as asymmetric catalyst, antibacterial, and mimic molecules during simulate biological processes, etc. In recent years, research on synthesis and properties of asymmetric Schiff bases have become an increase interest of chemists. This review summarizes asymmetric Schiff bases derived from diaminomaleonitrile (DAMN) and DAMN-based asymmetric Schiff bases metal complexes. Applications of DAMN-based asymmetric Schiff bases are also discussed in this review.

  6. Mechanistic Insights into Homogeneous and Heterogeneous Asymmetric Iron Catalysis

    Science.gov (United States)

    Sonnenberg, Jessica

    Our group has been focused on replacing toxic and expensive precious metal catalysts with iron for the synthesis of enantiopure compounds for industrial applications. During an investigation into the mechanism of asymmetric transfer hydrogenation with our first generation iron-(P-N-N-P) catalysts we found substantial evidence for zero-valent iron nanoparticles coated in chiral ligand acting as the active site. Extensive experimental and computational experiments were undertaken which included NMR, DFT, reaction profile analysis, substoichiometric poisoning, electron microscope imaging, XPS and multiphasic analysis, all of which supported the fact that NPs were the active species in catalysis. Reversibility of this asymmetric reaction on the nanoparticle surface was then probed using oxidative kinetic resolution of racemic alcohols, yielding modest enantiopurity and high turnover frequencies (TOF) for a range of aromatic alcohols. Efficient dehydrogenation of ammonia-borane for hydrogen evolution and the formation of B-N oligomers was also shown using the NP system, yielding highly active systems, with a maximum TOF of 3.66 H2/s-1 . We have also begun to focus on the development of iron catalysts for asymmetric direct hydrogenation of ketones using hydrogen gas. New chiral iron-(P-N-P) catalysts were developed and shown to be quite active and selective for a wide range of substrates. Mechanistic investigations primarily using NMR and DFT indicated that a highly active trans-dihydride species was being formed during catalyst activation. Lastly, a new library of chiral P-N-P and P-NH-P ligands were developed, as well as their corresponding iron complexes, some of which show promise for the development of future generations of active asymmetric direct hydrogenation catalysts.

  7. LG tools for asymmetric wargaming

    Science.gov (United States)

    Stilman, Boris; Yakhnis, Alex; Yakhnis, Vladimir

    2002-07-01

    Asymmetric operations represent conflict where one of the sides would apply military power to influence the political and civil environment, to facilitate diplomacy, and to interrupt specified illegal activities. This is a special type of conflict where the participants do not initiate full-scale war. Instead, the sides may be engaged in a limited open conflict or one or several sides may covertly engage another side using unconventional or less conventional methods of engagement. They may include peace operations, combating terrorism, counterdrug operations, arms control, support of insurgencies or counterinsurgencies, show of force. An asymmetric conflict can be represented as several concurrent interlinked games of various kinds: military, transportation, economic, political, etc. Thus, various actions of peace violators, terrorists, drug traffickers, etc., can be expressed via moves in different interlinked games. LG tools allow us to fully capture the specificity of asymmetric conflicts employing the major LG concept of hypergame. Hypergame allows modeling concurrent interlinked processes taking place in geographically remote locations at different levels of resolution and time scale. For example, it allows us to model an antiterrorist operation taking place simultaneously in a number of countries around the globe and involving wide range of entities from individuals to combat units to governments. Additionally, LG allows us to model all sides of the conflict at their level of sophistication. Intelligent stakeholders are represented by means of LG generated intelligent strategies. TO generate those strategies, in addition to its own mathematical intelligence, the LG algorithm may incorporate the intelligence of the top-level experts in the respective problem domains. LG models the individual differences between intelligent stakeholders. The LG tools make it possible to incorporate most of the known traits of a stakeholder, i.e., real personalities involved in

  8. Loan sales under asymmetric information

    OpenAIRE

    Vargas Martínez, Mónica

    2010-01-01

    Loans are illiquid assets that can be sold in a secondary market even that buyers have no certainty about their quality. I study a model in which a lender has access to new investment opportunities when all her assets are illiquid. To raise funds, the lender may either borrow using her assets as collateral, or she can sell them in a secondary market. Given asymmetric information about assets quality, the lender cannot recover the total value of her assets. There is then a role for the governm...

  9. Spontaneous baryogenesis from asymmetric inflaton

    Energy Technology Data Exchange (ETDEWEB)

    Takahashi, Fuminobu [Tohoku Univ., Sendai (Japan). Dept. of Physics; Tokyo Univ., Chiba (Japan). Kavli IPMU (WPI), UTIAS; Yamada, Masaki [Tokyo Univ., Chiba (Japan). Kavli IPMU (WPI), UTIAS; Tokyo Univ., Chiba (Japan). Inst. for Cosmic Ray Research; DESY Hamburg (Germany)

    2015-10-15

    We propose a variant scenario of spontaneous baryogenesis from asymmetric inflaton based on current-current interactions between the inflaton and matter fields with a non-zero B-L charge. When the inflaton starts to oscillate around the minimum after inflation, it may lead to excitation of a CP-odd component, which induces an effective chemical potential for the B-L number through the current-current interactions. We study concrete inflation models and show that the spontaneous baryogenesis scenario can be naturally implemented in the chaotic inflation in supergravity.

  10. Review of Composite Asymmetric Spur Gear

    OpenAIRE

    Sandeep C. Dhaduti; Dr. S. G. Sarganachari

    2015-01-01

    Gears made from composite materials are widely used in many power and motion transmission applications. Due to lower weight to stiffness ratio, composite gears may be replaced by conventional material gears in power transmission systems. Design of gears with asymmetric teeth enables to increase load capacity, reduce weight, size and vibration level. This article includes a summary of asymmetric gear design parameters, new developments of asymmetric spur gear and their ...

  11. The asymmetric Goos-H\\"anchen effect

    OpenAIRE

    Araujo, Manoel P.; Carvalho, Silvânia A.; De Leo, Stefano

    2013-01-01

    We show in which conditions optical gaussian beams, propagating throughout an homogeneous dielectric right angle prism, present an asymmetric Goos-H\\"anchen (GH) effect. This asymmetric behavior is seen for incidence at critical angles and happens in the propagation direction of the outgoing beam. The asymmetric GH effect can be also seen as an amplification of the standard GH shift. Due to the fact that it only depends on the ratio between the wavelength and the minimal waist size of the inc...

  12. The asymmetric Goos-H\\"anchen effect

    CERN Document Server

    Araujo, Manoel P; De Leo, Stefano

    2014-01-01

    We show in which conditions optical gaussian beams, propagating throughout an homogeneous dielectric right angle prism, present an asymmetric Goos-H\\"anchen (GH) effect. This asymmetric behavior is seen for incidence at critical angles and happens in the propagation direction of the outgoing beam. The asymmetric GH effect can be also seen as an amplification of the standard GH shift. Due to the fact that it only depends on the ratio between the wavelength and the minimal waist size of the incoming gaussian beam, it can be also used to determine one of these parameters. Multiple peaks interference is an additional phenomenon seen in the presence of such asymmetric effects.

  13. Excitons in asymmetric quantum wells

    Science.gov (United States)

    Grigoryev, P. S.; Kurdyubov, A. S.; Kuznetsova, M. S.; Ignatiev, I. V.; Efimov, Yu. P.; Eliseev, S. A.; Petrov, V. V.; Lovtcius, V. A.; Shapochkin, P. Yu.

    2016-09-01

    Resonance dielectric response of excitons is studied for the high-quality InGaAs/GaAs heterostructures with wide asymmetric quantum wells (QWs). To highlight effects of the QW asymmetry, we have grown and studied several heterostructures with nominally square QWs as well as with triangle-like QWs. Several quantum confined exciton states are experimentally observed as narrow exciton resonances. A standard approach for the phenomenological analysis of the profiles is generalized by introducing different phase shifts for the light waves reflected from the QWs at different exciton resonances. Good agreement of the phenomenological fit to the experimentally observed exciton spectra for high-quality structures allowed us to reliably obtain parameters of the exciton resonances: the exciton transition energies, the radiative broadenings, and the phase shifts. A direct numerical solution of the Schrödinger equation for the heavy-hole excitons in asymmetric QWs is used for microscopic modeling of the exciton resonances. Remarkable agreement with the experiment is achieved when the effect of indium segregation is taken into account. The segregation results in a modification of the potential profile, in particular, in an asymmetry of the nominally square QWs.

  14. Thin lenses of asymmetric power

    Directory of Open Access Journals (Sweden)

    W. F. Harris

    2009-12-01

    Full Text Available It is generally supposed that thin systems, including refracting surfaces and thin lenses, have powers that are necessarily symmetric.  In other words they have powers which can be represented assymmetric dioptric power matrices and in the familar spherocylindrical form used in optometry and ophthalmology.  This paper shows that this is not correct and that it is indeed possible for a thin system to have a power that is not symmetric and which cannot be expressed in spherocylindrical form.  Thin systems of asymmetric power are illustratedby means of a thin lens that is modelled with small prisms and is chosen to have a dioptric power ma-trix that is antisymmetric.  Similar models can be devised for a thin system whose dioptric power matrix is any  2 2 ×  matrix.  Thus any power, symmetric, asymmetric or antisymmetric, is possible for a thin system.  In this sense our understanding of the power of thin systems is now complete.

  15. Asymmetric Laguerre-Gaussian beams

    Science.gov (United States)

    Kovalev, A. A.; Kotlyar, V. V.; Porfirev, A. P.

    2016-06-01

    We introduce a family of asymmetric Laguerre-Gaussian (aLG) laser beams. The beams have been derived via a complex-valued shift of conventional LG beams in the Cartesian plane. While propagating in a uniform medium, the first bright ring of the aLG beam becomes less asymmetric and the energy is redistributed toward peripheral diffraction rings. The projection of the orbital angular momentum (OAM) onto the optical axis is calculated. The OAM is shown to grow quadratically with increasing asymmetry parameter of the aLG beam, which equals the ratio of the shift to the waist radius. Conditions for the OAM becoming equal to the topological charge have been derived. For aLG beams with zero radial index, we have deduced an expression to define the intensity maximum coordinates and shown the crescent-shaped intensity pattern to rotate during propagation. Results of the experimental generation and rotation of aLG beams agree well with theoretical predictions.

  16. Biomimetically inspired asymmetric total synthesis of (+)-19-dehydroxyl arisandilactone A

    Science.gov (United States)

    Han, Yi-Xin; Jiang, Yan-Long; Li, Yong; Yu, Hai-Xin; Tong, Bing-Qi; Niu, Zhe; Zhou, Shi-Jie; Liu, Song; Lan, Yu; Chen, Jia-Hua; Yang, Zhen

    2017-01-01

    Complex natural products are a proven and rich source of disease-modulating drugs and of efficient tools for the study of chemical biology and drug discovery. The architectures of complex natural products are generally considered to represent significant barriers to efficient chemical synthesis. Here we describe a concise and efficient asymmetric synthesis of 19-dehydroxyl arisandilactone A--which belongs to a family of architecturally unique, highly oxygenated nortriterpenoids isolated from the medicinal plant Schisandra arisanensis. This synthesis takes place by means of a homo-Michael reaction, a tandem retro-Michael/Michael reaction, and Cu-catalysed intramolecular cyclopropanation as key steps. The proposed mechanisms for the homo-Michael and tandem retro-Michael/Michael reactions are supported by density functional theory (DFT) calculation. The developed chemistry may find application for the synthesis of its other family members of Schisandraceae nortriterpenoids.

  17. Biomimetically inspired asymmetric total synthesis of (+)-19-dehydroxyl arisandilactone A

    Science.gov (United States)

    Han, Yi-Xin; Jiang, Yan-Long; Li, Yong; Yu, Hai-Xin; Tong, Bing-Qi; Niu, Zhe; Zhou, Shi-Jie; Liu, Song; Lan, Yu; Chen, Jia-Hua; Yang, Zhen

    2017-01-01

    Complex natural products are a proven and rich source of disease-modulating drugs and of efficient tools for the study of chemical biology and drug discovery. The architectures of complex natural products are generally considered to represent significant barriers to efficient chemical synthesis. Here we describe a concise and efficient asymmetric synthesis of 19-dehydroxyl arisandilactone A—which belongs to a family of architecturally unique, highly oxygenated nortriterpenoids isolated from the medicinal plant Schisandra arisanensis. This synthesis takes place by means of a homo-Michael reaction, a tandem retro-Michael/Michael reaction, and Cu-catalysed intramolecular cyclopropanation as key steps. The proposed mechanisms for the homo-Michael and tandem retro-Michael/Michael reactions are supported by density functional theory (DFT) calculation. The developed chemistry may find application for the synthesis of its other family members of Schisandraceae nortriterpenoids. PMID:28139648

  18. Asymmetric Price Transmission in Food Supply Chains: Impulse Response Analysis by Local Projections Applied to U.S. Broiler and Pork Prices

    NARCIS (Netherlands)

    Kuiper, W.E.; Oude Lansink, A.G.J.M.

    2013-01-01

    In this article, the author's set out Jordà's (2005) method of local projections by which nonlinear/ asymmetric impulse responses can be computed without the need to specify and estimate the underlying nonlinear/asymmetric dynamic system. The method is used to compute price-reaction functions that s

  19. Mechanistic insights on cooperative asymmetric multicatalysis using chiral counterions.

    Science.gov (United States)

    Jindal, Garima; Sunoj, Raghavan B

    2014-08-15

    Cooperative multicatalytic methods are steadily gaining popularity in asymmetric catalysis. The use of chiral Brønsted acids such as phosphoric acids in conjunction with a range of transition metals has been proven to be effective in asymmetric synthesis. However, the lack of molecular-level understanding and the accompanying ambiguity on the role of the chiral species in stereoinduction continues to remain an unresolved puzzle. Herein, we intend to disclose some novel transition state models obtained through DFT(B3LYP and M06) computations for a quintessential reaction in this family, namely, palladium-catalyzed asymmetric Tsuji-Trost allylation of aldehydes. The aldehyde is activated as an enamine by the action of a secondary amine (organocatalysis), which then adds to an activated Pd-allylic species (transition metal catalysis) generated through the protonation of allyic alcohol by chiral BINOL-phosphoric acid (Brønsted acid catalysis). We aim to decipher the nature of chiral BINOL-phosphates and their role in creating a quaternary chiral carbon atom in this triple catalytic system. The study reports the first transition state model capable of rationalizing chiral counterion-induced enantioselectivity. It is found that the chiral phosphate acts as a counterion in the stereocontrolling event rather than the conventional ligand mode.

  20. Worst Asymmetrical Short-Circuit Current

    DEFF Research Database (Denmark)

    Arana Aristi, Iván; Holmstrøm, O; Grastrup, L

    2010-01-01

    In a typical power plant, the production scenario and the short-circuit time were found for the worst asymmetrical short-circuit current. Then, a sensitivity analysis on the missing generator values was realized in order to minimize the uncertainty of the results. Afterward the worst asymmetrical...

  1. Renewable resource management under asymmetric information

    DEFF Research Database (Denmark)

    Jensen, Frank; Andersen, Peder; Nielsen, Max

    2013-01-01

    Asymmetric information between fishermen and the regulator is important within fisheries. The regulator may have less information about stock sizes, prices, costs, effort, productivity and catches than fishermen. With asymmetric information, a strong analytical tool is principal-agent analysis. I...

  2. Induced axial chirality in biocatalytic asymmetric ketone reduction.

    Science.gov (United States)

    Agudo, Rubén; Roiban, Gheorghe-Doru; Reetz, Manfred T

    2013-02-06

    Catalytic asymmetric reduction of prochiral ketones of type 4-alkylidene cyclohexanone with formation of the corresponding axially chiral R-configurated alcohols (up to 99% ee) was achieved using alcohol dehydrogenases, whereas chiral transition-metal catalysts fail. Reversal of enantioselectivity proved to be possible by directed evolution based on saturation mutagenesis (up to 98% ee (S)). Utilization of ketone with a vinyl bromide moiety allows respective R- and S-alcohols to be exploited as key compounds in Pd-catalyzed cascade reactions.

  3. Preparation of D-Phenylalanine by Asymmetric Transformation

    Institute of Scientific and Technical Information of China (English)

    Ben Mei WEI; Li Jian JIANG; Ying Ping ZHENG; Hai Qing XU

    2004-01-01

    The method of preparing D-phenylalanine by asymmetric transformation is reported.D-phenylalanine was prepared from DL-phenylalanine by two-step reaction.D-phenylalanine(2S,3S)-tartrate was prepared by heating DL-phenylalanine, salicylaldehyde,and(2S,3S)-tartaric acid in propionic acid;the obtained D-phenylalanine(2S,3S)-tartrate was treated with triethylamine in ethanol giving D-phenylalanine with 98% optical purity in 69% yield.

  4. Biocatalytic asymmetric phosphorylation of mevalonate

    NARCIS (Netherlands)

    Matsumi, R.; Hellriegel, C.; Schoenenberger, B.; Milesi, T.; Oost, van der J.; Wohlgemuth, R.

    2014-01-01

    The excellent selectivity of the mevalonate kinase-catalyzed phosphorylation of mevalonate simplifies lengthy multi-step routes to (R)-mevalonate-5-phosphate to a one-step biocatalytic reaction, because the phosphate group can be transferred directly and without any additional reaction steps

  5. Asymmetric Syntheses Aided by Biocatalysts

    Institute of Scientific and Technical Information of China (English)

    陈沛然; 顾建新; 魏志亮; 韩世清; 李祖义; 林国强

    2003-01-01

    This article summarizes the achievements of the authors' group in the area of biocatalyst-catalyzed organic reactions in recent 10 years. A strain of Geotrichum sp. obtained by screeninu is capable of stereoselectlvely reducing a number of carbonyl compounds. In many cases, the stermghemistry is complementary with that obtained by baker' s yeast. Therefore, this microorganism provides a useful pathway to the preparation of alcohol eompounds with specific configurations. On the other hand, a nmmber of plant sourees have been screened for oxynitrilases and the hydrocyanation reactions of various arylcarboxalde-hydes have been investigated.A"micro-aqueous reaction system" was invented,by which a serles of novel optically active cyanohydrins were prepared.On this hasis,a high through-put comtimasous reaction system has been designed.This paper also deseribes examples of the syntheses of bio-active compounds by using the optieally active compounds obtained from the above mentioned catalytic reactions as precursors.

  6. Condensation on Slippery Asymmetric Bumps

    CERN Document Server

    Park, Kyoo-Chul; He, Neil; Aizenberg, Joanna

    2015-01-01

    Bumps are omnipresent from human skin to the geological structures on planets, which offer distinct advantages in numerous phenomena including structural color, drag reduction, and extreme wettability. Although the topographical parameters of bumps such as radius of curvature of convex regions significantly influence various phenomena including anti-reflective structures and contact time of impacting droplets, the effect of the detailed bump topography on growth and transport of condensates have not been clearly understood. Inspired by the millimetric bumps of the Namib Desert beetle, here we report the identified role of radius of curvature and width of bumps with homogeneous surface wettability in growth rate, coalescence and transport of water droplets. Further rational design of asymmetric convex topography and synergetic combination with slippery coating simultaneously enable self-transport, leading to unseen five-fold higher growth rate and an order of magnitude faster shedding time of droplets compared...

  7. Research on asymmetric searchable encryption

    Science.gov (United States)

    Yu, Zonghua; Wu, Yudong

    2017-05-01

    Cloud server side to ease the user's local storage pressure at the same time, there are hidden data on the hidden dangers, the user often choose to upload the data in the form of cipher text to the cloud server. However, the classic data encryption and decryption algorithms are not provided search function, affecting the user's efficiency. To this end, an asymmetric searchable encryption scheme is proposed. The scheme can be used for any person can generate a trapdoor, cipher text can be free modified, the key pair generated by the user themselves, encrypt the identity, S-shaped virtual and other five loopholes to improve. The analysis results show that the scheme solves the above five vulnerabilities in the original scheme, so that the information semantics of both parties of communication can be guaranteed.

  8. Development of chiral metal amides as highly reactive catalysts for asymmetric [3 + 2] cycloadditions

    Science.gov (United States)

    Yamashita, Yasuhiro; Yoshimoto, Susumu; Dutton, Mark J

    2016-01-01

    Summary Highly efficient catalytic asymmetric [3 + 2] cycloadditions using a chiral copper amide are reported. Compared with the chiral CuOTf/Et3N system, the CuHMDS system showed higher reactivity, and the desired reactions proceeded in high yields and high selectivities with catalyst loadings as low as 0.01 mol %. PMID:27559396

  9. Asymmetric Cyclization of N-Sulfonyl Alkenyl Amides Catalyzed by Iridium/Chiral Diene Complexes.

    Science.gov (United States)

    Nagamoto, Midori; Yanagi, Tomoyuki; Nishimura, Takahiro; Yorimitsu, Hideki

    2016-09-16

    Iridium/chiral diene complexes efficiently catalyzed the asymmetric cyclization of N-sulfonyl alkenyl amides to give the corresponding 2-pyrrolidone derivatives with high enantioselectivity. A mechanistic study revealed that the reaction proceeds via nucleophilic attack of the amide on the alkene moiety.

  10. De novo formal synthesis of (-)-virginiamycin M2 via the asymmetric hydration of dienoates.

    Science.gov (United States)

    Mortensen, Matthew S; Osbourn, Joshua M; O'Doherty, George A

    2007-08-02

    A de novo approach to the formal total synthesis of the macrolide natural product (-)-virginiamycin M2 has been achieved via a convergent approach. The absolute and relative stereochemistry of the nonpeptide portion of (-)-virginiamycin M2 was introduced by two Sharpless asymmetric dihydroxylation reactions.

  11. The Nonlinear Phillips Curve and Inflation Forecast Targeting - Symmetric Versus Asymmetric Monetary Policy Rules

    NARCIS (Netherlands)

    Schaling, E.

    1998-01-01

    We extend the Svensson (1997a) inflation forecast targeting framework with a convex Phillips curve. We derive an asymmetric target rule, that implies a higher level of nominal interest rates than the Svensson (1997a) forward looking version of the reaction function popularised by Taylor (1993).

  12. Amino acids as chiral anionic ligands for ruthenium based asymmetric olefin metathesis.

    Science.gov (United States)

    Ivry, Elisa; Ben-Asuly, Amos; Goldberg, Israel; Lemcoff, N Gabriel

    2015-03-01

    Several amino acid ligands were introduced into the Hoveyda-Grubbs 2nd generation complex by a facile anionic ligand exchange. The chiral pre-catalysts obtained displayed enantioselectivity in asymmetric ring-closing and ring-opening cross-metathesis reactions. Reduction of the lability of the carboxylate ligands was found to be cardinal for improving the observed enantiomeric product enrichment.

  13. Palladium-Catalyzed Asymmetric [3+2] Cycloaddition of Trimethylenemethane with Imines

    Science.gov (United States)

    Trost, Barry M.; Silverman, Steven M.; Stambuli, James P.

    2008-01-01

    The transition metal catalyzed trimethylenemethane [3+2] cycloaddition provides a direct route to functionalized heterocycles. Herein, we describe a catalytic, asymmetric protocol for the reaction between 3-acetoxy-2-trimethylsilylmethyl-1-propene and various imines. The corresponding pyrrolidines were obtained in excellent yields and enantioselectivities making use of the novel phosphoramidite L10. PMID:17887679

  14. Organocatalysts immobilised onto gold nanoparticles: application in the asymmetric reduction of imines with trichlorosilane.

    Science.gov (United States)

    Malkov, Andrei V; Figlus, Marek; Cooke, Graeme; Caldwell, Stuart T; Rabani, Gouher; Prestly, Mark R; Kocovský, Pavel

    2009-05-07

    Gold nanoparticles functionalised with a valine-derived formamide have been developed as effective homogenous catalysts for the asymmetric reduction of ketimine 1 with trichlorosilane (< or = 84% ee) in toluene. This methodology both simplifies the recovery of the catalyst and its separation from the product, as the nanoparticles can be readily removed and subsequently recycled by precipitation from the reaction mixture.

  15. The Nonlinear Phillips Curve and Inflation Forecast Targeting - Symmetric Versus Asymmetric Monetary Policy Rules

    NARCIS (Netherlands)

    Schaling, E.

    1998-01-01

    We extend the Svensson (1997a) inflation forecast targeting framework with a convex Phillips curve. We derive an asymmetric target rule, that implies a higher level of nominal interest rates than the Svensson (1997a) forward looking version of the reaction function popularised by Taylor (1993). Exte

  16. A kinetic and structural investigation of DNA-Based asymmetric catalysis using first-generation ligands

    NARCIS (Netherlands)

    Rosati, Fiora; Boersma, Arnold J.; Klijn, Jaap E.; Meetsma, Auke; Feringa, Ben L.; Roelfes, Gerard

    2009-01-01

    The recently developed concept of DNA-based asymmetric catalysis involves the transfer of chirality from the DNA double helix in reactions using a noncovalently bound catalyst. To date, two generations of DNA-based catalysts have been reported that differ in the design of the ligand for the metal. H

  17. Allenylphosphonates with a 1,3,2-dioxaphosphorinane ring: Synthesis, structures, stability and utility

    Indian Academy of Sciences (India)

    N N Bhuvan Kumar; Manab Chakravarty; N Satish Kumar; K V Sajna; K C Kumara Swamy

    2009-01-01

    Synthesis, structures and stability (thermal and air) of allenylphosphonates of the type (OCH2CMe2CH2O)P(O)C(R)=C=CR'R" and [R"R'C=C=C(R)P(O)(OCH2)2]2C are discussed. Thermally activated dimerization (cycloaddition) of (OCH2CMe2CH2O)P(O)C(H)=C=CMe2 leads to the phosphonocyclobutane [(OCH2CMe2CH2O)P(O)C(H)=]2[C-CMe2]2 (18). Many of these allenes undergo addition of diethylamine to lead to enaminophosphonates that are readily hydrolysed by water to lead to -ketophosphonates. The latter compounds are useful as Horner-Wadsworth-Emmons (HWE) reagents. Molecular structures of (OCH2CMe2CH2O)P(O)C(CH2OH)=C=CH2 (6), [H2C=C=C(H)P(O)(OCH2)2]2C (9), (OCH2CMe2CH2O)P(O)CH=C=CH2 (12), [(OCH2CMe2CH2O)P(O)C(H)=]2[C-CMe2]2 (18), and the -ketophosphonate (OCH2CMe2CH2O)P(O)CH2)-C(O)CHMe2 (24) have been determined. In compound 6, intermolecular hydrogen bonding between the phosphoryl oxygen and the hydroxyl group leading to an infinite chain is observed. In 6, there is a significant deviation (ca 7°) from the orthogonality expected between the planes containing 4 atoms of (a) H2C=C and (b) C=C(H)P in the allene part. In 9, weak C-H…O interaction between the phosphoryl oxygen atom and a CH2 proton of the six-membered ring is present.

  18. An Asymmetric Synthetic Approach to the A-ring of the Taxol Family of Anti-Cancer Compounds

    Directory of Open Access Journals (Sweden)

    M. L. Marin

    1998-02-01

    Full Text Available A synthetic route developed for the preparation of the A-ring of Taxol family of molecules is reported. By means of an intramolecular Diels-Alder reaction an asymmetric approach to this ring has been accomplished. Also, initial studies to prepare the A ring using an intramolecular Diels-Alder reaction have been successful.

  19. Synthesis of New Bifunctional Bis(oxazolines) and Their Application in the Asymmetric Cyanosilylation of Aromatic Ketones

    Institute of Scientific and Technical Information of China (English)

    LUO,Mei; DU,Da-Ming

    2004-01-01

    @@ Catalytic asymmetric synthesis of tertiary cyanohydrins by the addition of cyanide to a wide range of ketones has important synthetic utility, since the resulting optically active cyanohydrins are important intermediates for the synthesis of a variety of valuable classes of chiral compounds. The application of oxazoline in asymmetric cyanosilylation has seldom reported in comparation with other reactions.[1] Recently, polymer-supported pyridine-bis(oxazoline) ytterbium complex was reported to catalyze cyanosilylation of benzaldehyde.

  20. Non-Classical C–H···X Hydrogen Bonding and Its Role in Asymmetric Organocatalysis

    KAUST Repository

    Ajitha, Manjaly John

    2016-08-17

    Non-classical hydrogen bonds (NCHBs) have attracted significant interest in the past decade particularly because of their important role in asymmetric catalytic systems. These weak interactions (< 4 kcal/mol) offer much flexibility in the preorganization of molecular entities required to achieve high enantioselectivity. Herein, we review some recent important organocatalytic asymmetric reactions where a NCHB serves as a critical factor in determining the stereoselectivity.

  1. Asymmetric Michael Addition of Activated Alkenes to Nitro Alkenes Catalyzed by Organic Catalyst

    Institute of Scientific and Technical Information of China (English)

    XUE Dong; CHEN Yong-Chun; CUI Xin; WANG Qi-Wei; ZHU Jin; DENG Jin-Gen

    2003-01-01

    @@ Enantioselective Michael addition is one of the most powerfulbond-forming reaction in organic synthesis. [1] A mong the Michael acceptors, nitro alkenes are very attractive, because the nitro group is the most electron-withdrawing group known and it can serve as masked functionality to be further transformed after the addition has taken place. [2] Recently, asymmetric Michael reactions catalyzed by organic catalyst have draw much attention.[3

  2. Microwave-induced inactivation of DNA-based hybrid catalyst in asymmetric catalysis.

    Science.gov (United States)

    Zhao, Hua; Shen, Kai

    2016-03-01

    DNA-based hybrid catalysts have gained strong interests in asymmetric reactions. However, to maintain the high enantioselectivity, these reactions are usually conducted at relatively low temperatures (e.g. DNA-based hybrid catalyst even at low temperatures (such as 5 °C). Circular dichroism (CD) spectra and gel electrophoresis of DNA suggest that microwave exposure degrades DNA molecules and disrupts DNA double-stranded structures, causing changes of DNA-metal ligand binding properties and thus poor DNA catalytic performance.

  3. Enantioselective Synthesis of All-Carbon Quaternary Stereogenic Centers via Copper-Catalyzed Asymmetric Allylic Alkylation of (Z)-Allyl Bromides with Organolithium Reagents

    NARCIS (Netherlands)

    Fananas-Mastral, Martin; Vitale, Romina; Perez, Manuel; Feringa, Ben L.

    2015-01-01

    A copper/phosphoramidite catalyzed asymmetric allylic alkylation of Z trisubstituted allyl bromides with organolithium reagents is reported. The reaction affords all-carbon quaternary stereogenic centers in high yields and very good regio- and enantioselectivity. This systematic study illustrates

  4. Asymmetric dark matter in braneworld cosmology

    Energy Technology Data Exchange (ETDEWEB)

    Meehan, Michael T.; Whittingham, Ian B., E-mail: Michael.Meehan@my.jcu.edu.au, E-mail: Ian.Whittingham@jcu.edu.au [School of Engineering and Physical Sciences, James Cook University, Townsville, 4811 Australia (Australia)

    2014-06-01

    We investigate the effect of a braneworld expansion era on the relic density of asymmetric dark matter. We find that the enhanced expansion rate in the early universe predicted by the Randall-Sundrum II (RSII) model leads to earlier particle freeze-out and an enhanced relic density. This effect has been observed previously by Okada and Seto (2004) for symmetric dark matter models and here we extend their results to the case of asymmetric dark matter. We also discuss the enhanced asymmetric annihilation rate in the braneworld scenario and its implications for indirect detection experiments.

  5. Asymmetric stem cell division: lessons from Drosophila.

    Science.gov (United States)

    Wu, Pao-Shu; Egger, Boris; Brand, Andrea H

    2008-06-01

    Asymmetric cell division is an important and conserved strategy in the generation of cellular diversity during animal development. Many of our insights into the underlying mechanisms of asymmetric cell division have been gained from Drosophila, including the establishment of polarity, orientation of mitotic spindles and segregation of cell fate determinants. Recent studies are also beginning to reveal the connection between the misregulation of asymmetric cell division and cancer. What we are learning from Drosophila as a model system has implication both for stem cell biology and also cancer research.

  6. Regenerating a symmetry in asymmetric dark matter.

    Science.gov (United States)

    Buckley, Matthew R; Profumo, Stefano

    2012-01-06

    Asymmetric dark matter theories generically allow for mass terms that lead to particle-antiparticle mixing. Over the age of the Universe, dark matter can thus oscillate from a purely asymmetric configuration into a symmetric mix of particles and antiparticles, allowing for pair-annihilation processes. Additionally, requiring efficient depletion of the primordial thermal (symmetric) component generically entails large annihilation rates. We show that unless some symmetry completely forbids dark matter particle-antiparticle mixing, asymmetric dark matter is effectively ruled out for a large range of masses, for almost any oscillation time scale shorter than the age of the Universe.

  7. On-chip asymmetric microcavity optomechanics.

    Science.gov (United States)

    Soltani, Soheil; Hudnut, Alexa W; Armani, Andrea M

    2016-12-26

    High quality factor (Q) optical resonators have enabled rapid growth in the field of cavity-enhanced, radiation pressure-induced optomechanics. However, because research has focused on axisymmetric devices, the observed regenerative excited mechanical modes are similar. In the present work, a strategy for fabricating high-Q whispering gallery mode microcavities with varying degrees of asymmetry is developed and demonstrated. Due to the combination of high optical Q and asymmetric device design, two previously unobserved modes, the asymmetric cantilever and asymmetric crown mode, are demonstrated with sub-mW thresholds for onset of oscillations. The experimental results are in good agreement with computational modeling predictions.

  8. Asymmetric autocatalysis of pyrimidyl alkanol and its application to the study on the origin of homochirality.

    Science.gov (United States)

    Soai, Kenso; Kawasaki, Tsuneomi; Matsumoto, Arimasa

    2014-12-16

    CONSPECTUS: Amplification of enantiomeric excess (ee) is a key feature for the chemical evolution of biological homochirality from the origin of chirality. We describe the amplification of ee in the asymmetric autocatalysis of 5-pyrimidyl alkanols in the reaction between diisopropylzinc (i-Pr2Zn) and pyrimidine-5-carbaldehydes. During the reaction, an extremely low ee (ca. 0.00005% ee) can be amplified to >99.5% ee, and therefore, the initial slightly major enantiomer is automultiplied by a factor of ca. 630000, while the initial slightly minor enantiomer is automultiplied by a factor of less than 1000. In addition, pyrimidyl alkanols with various substituents at the 2-position of the pyrimidine ring, 3-quinolyl alkanol, 5-carbamoyl-3-pyridyl alkanol, and large multifunctionalized pyrimidyl alkanols also act as highly efficient asymmetric autocatalysts in the addition of i-Pr2Zn to the corresponding aldehydes. The asymmetric autocatalysis of pyrimidyl alkanol can discriminate the chirality of various compounds. Chiral substances such as alcohols, amino acids, hydrocarbons, metal complexes, and heterogeneous chiral materials can act as chiral triggers for asymmetric autocatalysis to afford pyrimidyl alkanols with the corresponding absolute configuration of the initiator. This recognition ability of chiral compounds is extremely high, and chiral discrimination of a cryptochiral quaternary saturated hydrocarbon was established by applying asymmetric autocatalysis. By using the large amplification effect of the asymmetric autocatalysis, we can link various proposed origins of chirality with highly enantioenriched organic compounds in conjunction with asymmetric autocatalysis. Thus, a statistical fluctuation in ee of racemic compounds can be amplified to high ee by using asymmetric autocatalysis. Enantiomeric imbalance induced by irradiation of circularly polarized light can affect the enantioselectivity of asymmetric autocatalysis. The asymmetric autocatalysis was also

  9. an asymmetrically heated rectangular minichannel

    Directory of Open Access Journals (Sweden)

    Strąk Kinga

    2017-01-01

    Full Text Available This paper discusses test results concerning flow boiling heat transfer in a minichannel 1.7 mm in depth, 16 mm in width and 180 mm in length. The essential part of the experimental stand was a vertically oriented rectangular minichannel, which was heated asymmetrically with a plate made of Haynes-230 alloy. Distilled water was used as the cooling fluid. Changes in the temperature on the outer side of the heated plate in the central, axially symmetric part of the channel were measured using infrared thermography. Simultaneously, the other side of the heated plate in contact with the fluid was observed through a glass pane to identify the two-phase flow patterns. The one-dimensional model used for the heat transfer analysis took into account the heat flow direction, which was perpendicular to the direction of the fluid flow in the minichannel. The study involved determining local values of the heat transfer coefficient and generating boiling curves. The data for water were compared with the findings reported for the FC-72 fluid.

  10. Force on an Asymmetric Capacitor

    CERN Document Server

    Bahder, T B; Bahder, Thomas B.; Fazi, Chris

    2002-01-01

    When a high voltage (~30 kV) is applied to a capacitor whose electrodes have different physical dimensions, the capacitor experiences a net force toward the smaller electrode (Biefeld-Brown effect). We have verified this effect by building four capacitors of different shapes. The effect may have applications to vehicle propulsion and dielectric pumps. We review the history of this effect briefly through the history of patents by Thomas Townsend Brown. At present, the physical basis for the Biefeld-Brown effect is not understood. The order of magnitude of the net force on the asymmetric capacitor is estimated assuming two different mechanisms of charge conduction between its electrodes: ballistic ionic wind and ionic drift. The calculations indicate that ionic wind is at least three orders of magnitude too small to explain the magnitude of the observed force on the capacitor. The ionic drift transport assumption leads to the correct order of magnitude for the force, however, it is difficult to see how ionic dr...

  11. Asymmetric dark matter bound state

    Science.gov (United States)

    Bi, Xiao-Jun; Kang, Zhaofeng; Ko, P.; Li, Jinmian; Li, Tianjun

    2017-02-01

    We propose an interesting framework for asymmetric scalar dark matter (ADM), which has novel collider phenomenology in terms of an unstable ADM bound state (ADMonium) produced via Higgs portals. ADMonium is a natural consequence of the basic features of ADM: the (complex scalar) ADM is charged under a dark local U (1 )d symmetry which is broken at a low scale and provides a light gauge boson X . The dark gauge coupling is strong and then ADM can annihilate away into X -pair effectively. Therefore, the ADM can form a bound state due to its large self-interaction via X mediation. To explore the collider signature of ADMonium, we propose that ADM has a two-Higgs doublet portal. The ADMonium can have a sizable mixing with the heavier Higgs boson, which admits a large cross section of ADMonium production associated with b b ¯. The resulting signature at the LHC depends on the decays of X . In this paper we consider a case of particular interest: p p →b b ¯ +ADMonium followed by ADMonium→2 X →2 e+e- where the electrons are identified as (un)converted photons. It may provide a competitive explanation to heavy di-photon resonance searches at the LHC.

  12. Twin Higgs Asymmetric Dark Matter.

    Science.gov (United States)

    García García, Isabel; Lasenby, Robert; March-Russell, John

    2015-09-18

    We study asymmetric dark matter (ADM) in the context of the minimal (fraternal) twin Higgs solution to the little hierarchy problem, with a twin sector with gauged SU(3)^{'}×SU(2)^{'}, a twin Higgs doublet, and only third-generation twin fermions. Naturalness requires the QCD^{'} scale Λ_{QCD}^{'}≃0.5-20  GeV, and that t^{'} is heavy. We focus on the light b^{'} quark regime, m_{b^{'}}≲Λ_{QCD}^{'}, where QCD^{'} is characterized by a single scale Λ_{QCD}^{'} with no light pions. A twin baryon number asymmetry leads to a successful dark matter (DM) candidate: the spin-3/2 twin baryon, Δ^{'}∼b^{'}b^{'}b^{'}, with a dynamically determined mass (∼5Λ_{QCD}^{'}) in the preferred range for the DM-to-baryon ratio Ω_{DM}/Ω_{baryon}≃5. Gauging the U(1)^{'} group leads to twin atoms (Δ^{'}-τ^{'}[over ¯] bound states) that are successful ADM candidates in significant regions of parameter space, sometimes with observable changes to DM halo properties. Direct detection signatures satisfy current bounds, at times modified by dark form factors.

  13. Sodium chlorite as an efficient oxidant and hydroxy ion pump in osmium-catalyzed asymmetric dihydroxylation.

    Science.gov (United States)

    Junttila, Mikko H; Hormi, Osmo E O

    2004-07-09

    Sodium chlorite is an efficient stoichiometric oxidant in Sharpless asymmetric dihydroxylation. One sodium chlorite provides the reaction with the stoichiometric number of electrons and hydroxide ions needed to dihydroxylate two olefins without the consumption of any additional base. 100% conversion in sodium chlorite asymmetric dihydroxylation of styrene was achieved twice as fast as in the established Sharpless K(3)[Fe(CN)(6)] dihydroxylation. Even internal olefins were dihydroxylated fast with sodium chlorite without hydrolysis aids. Eight olefins were dihydroxylated to corresponding vicinal diols with yields and ees as good as those reported in the literature for other similar processes.

  14. Asymmetric Swiss-cheese brane-worlds

    CERN Document Server

    Gergely, L A; K\\'{e}p\\'{\\i}r\\'{o}, Ibolya

    2006-01-01

    We consider Swiss-cheese brane universes embedded asymmetrically into the bulk. Neither the junction conditions between the Schwarzschild spheres and the sorrounding Friedmann brane regions with cosmological constant $\\Lambda $, nor the evolution of the scale factor are changed with respect to the symmetric case. The universe expands and decelerates forever. The asymmetry however has a drastic influence on the evolution of the cosmological fluid. Instead of the two branches of the symmetric case, in the asymmetric case four branches emerge. Moreover, the future pressure singularity arising in the symmetric case only for huge values of $\\Lambda $ becomes quite generic in the asymmetric case. Such pressure singularities emerge also when $\\Lambda=0$ is set. Then they are due entirely to the asymmetric embedding. For generic values of $\\Lambda $ we introduce a critical value of a suitably defined asymmetry parameter, which separates Swiss-cheese cosmologies with and without pressure singularities.

  15. Congenital asymmetric crying face: a case report

    Directory of Open Access Journals (Sweden)

    Semra Kara

    2011-12-01

    Full Text Available Congenital asymmetric crying face is an anomalia caused by unilateral absence or weakness of depressor anguli oris muscle The major finding of the disease is the absence or weakness in the outer and lower movement of the commissure during crying. The other expression muscles are normal and the face is symmetric at rest. The asymmetry in congenital asymmetric crying face is most evident during infancy but decreases by age. Congenital asymmetric crying face can be associated with cervicofacial, musclebone, respiratory, genitourinary and central nervous system anomalia. It is diagnosed by physical examination. This paper presents a six days old infant with Congenital asymmetric crying face and discusses the case in terms of diagnosis and disease features.

  16. Catalytic Asymmetric Synthesis of Phosphine Boronates

    NARCIS (Netherlands)

    Hornillos, Valentin; Vila, Carlos; Otten, Edwin; Feringa, Ben L.

    2015-01-01

    The first catalytic enantioselective synthesis of ambiphilic phosphine boronate esters is presented. The asymmetric boration of ,-unsaturated phosphine oxides catalyzed by a copper bisphosphine complex affords optically active organoboronate esters that bear a vicinal phosphine oxide group in good y

  17. Asymmetric Watermarking Scheme Based on Correlation Testing

    Directory of Open Access Journals (Sweden)

    Rinaldi Munir

    2007-06-01

    Full Text Available Abstract Asymmetric watermarking is the second generation of watermarking scheme which uses different keys for embedding and detecting watermark. Key for embedding is private or secret, but key for detecting can be available publicly and everyone who has the key can detect watermark Watermark detection does not need to be original multimedia data. Detection of watermark is realized using correlation test between public key and multimedia data received. In most of schemes, private key is the watermark itself; public key is public watermark which correlates to the private watermark This paper presents concept of asymmetric watermarking scheme that based on correlation test and reviews some schemes of asymmetric watermarking that have been proposed by researchers. Keywords: asymmetric watermarking, private key, public key, watermark., multimeelia,:correlation.

  18. A novel asymmetric synthesis of cinacalcet hydrochloride

    OpenAIRE

    Arava, Veera R; Laxminarasimhulu Gorentla; Pramod K. Dubey

    2012-01-01

    A novel route to asymmetric synthesis of cinacalcet hydrochloride by the application of (R)-tert-butanesulfinamide and regioselective N-alkylation of the naphthyl ethyl sulfinamide intermediate is described.

  19. A novel asymmetric synthesis of cinacalcet hydrochloride

    Directory of Open Access Journals (Sweden)

    Veera R. Arava

    2012-08-01

    Full Text Available A novel route to asymmetric synthesis of cinacalcet hydrochloride by the application of (R-tert-butanesulfinamide and regioselective N-alkylation of the naphthyl ethyl sulfinamide intermediate is described.

  20. A novel asymmetric synthesis of cinacalcet hydrochloride

    Science.gov (United States)

    Gorentla, Laxminarasimhulu; Dubey, Pramod K

    2012-01-01

    Summary A novel route to asymmetric synthesis of cinacalcet hydrochloride by the application of (R)-tert-butanesulfinamide and regioselective N-alkylation of the naphthyl ethyl sulfinamide intermediate is described. PMID:23019473

  1. Asymmetric cryptography based on wavefront sensing.

    Science.gov (United States)

    Peng, Xiang; Wei, Hengzheng; Zhang, Peng

    2006-12-15

    A system of asymmetric cryptography based on wavefront sensing (ACWS) is proposed for the first time to our knowledge. One of the most significant features of the asymmetric cryptography is that a trapdoor one-way function is required and constructed by analogy to wavefront sensing, in which the public key may be derived from optical parameters, such as the wavelength or the focal length, while the private key may be obtained from a kind of regular point array. The ciphertext is generated by the encoded wavefront and represented with an irregular array. In such an ACWS system, the encryption key is not identical to the decryption key, which is another important feature of an asymmetric cryptographic system. The processes of asymmetric encryption and decryption are formulized mathematically and demonstrated with a set of numerical experiments.

  2. Switchable regioselectivity in amine-catalysed asymmetric cycloadditions

    Science.gov (United States)

    Zhou, Zhi; Wang, Zhou-Xiang; Zhou, Yuan-Chun; Xiao, Wei; Ouyang, Qin; Du, Wei; Chen, Ying-Chun

    2017-06-01

    Building small-molecule libraries with structural and stereogenic diversity plays an important role in drug discovery. The development of switchable intermolecular cycloaddition reactions from identical substrates in different regioselective fashions would provide an attractive protocol. However, this also represents a challenge in organic chemistry, because it is difficult to control regioselectivity to afford the products exclusively and at the same time achieve high levels of stereoselectivity. Here, we report the diversified cycloadditions of α‧-alkylidene-2-cyclopentenones catalysed by cinchona-derived primary amines. An asymmetric γ,β‧-regioselective intermolecular [6+2] cycloaddition reaction with 3-olefinic (7-aza)oxindoles is realized through the in situ generation of formal 4-aminofulvenes, while a different β,γ-regioselective [2+2] cycloaddition reaction with maleimides to access fused cyclobutanes is disclosed. In contrast, an intriguing α,γ-regioselective [4+2] cycloaddition reaction is uncovered with the same set of substrates, by employing an unprecedented dual small-molecule catalysis of amines and thiols. All of the cycloaddition reactions exhibit excellent regio- and stereoselectivity, producing a broad spectrum of chiral architectures with high structural diversity and molecular complexity.

  3. Catalytic asymmetric generation of (Z)-disubstituted allylic alcohols.

    Science.gov (United States)

    Salvi, Luca; Jeon, Sang-Jin; Fisher, Ethan L; Carroll, Patrick J; Walsh, Patrick J

    2007-12-26

    A one-pot method for the direct preparation of enantioenriched (Z)-disubstituted allylic alcohols is introduced. Hydroboration of 1-halo-1-alkynes with dicyclohexylborane, reaction with t-BuLi, and transmetalation with dialkylzinc reagents generate (Z)-disubstituted vinylzinc intermediates. In situ reaction of these reagents with aldehydes in the presence of a catalyst derived from (-)-MIB generates (Z)-disubstituted allylic alcohols. It was found that the resulting allylic alcohols were racemic, most likely due to a rapid addition reaction promoted by LiX (X = Br and Cl). To suppress the LiX-promoted reaction, a series of inhibitors were screened. It was found that 20-30 mol % tetraethylethylenediamine inhibited LiCl without inhibiting the chiral zinc-based Lewis acid. In this fashion, (Z)-disubstituted allylic alcohols were obtained with up to 98% ee. The asymmetric (Z)-vinylation could be coupled with tandem diastereoselective epoxidation reactions to provide epoxy alcohols and allylic epoxy alcohols with up to three contiguous stereogenic centers, enabling the rapid construction of complex building blocks with high levels of enantio- and diastereoselectivity.

  4. DOES VOLATILITY RESPOND ASYMMETRIC TO PAST SHOCKS?

    OpenAIRE

    Claudiu Botoc

    2014-01-01

    The main aim of the paper is to examine if the stock market volatility exhibits asymmetric or an asymmetric response to past shocks, for certain CEE countries (Romania,Hungary, Bulgaria, Poland) over the period May 2004 - September 2014. For the stock marketsfrom East Europe the results are in line with the symmetric volatility, i.e. volatility is similaraffected by both positive and negative returns with the same magnitude. For the stock marketsfrom Central Europe the results are consistent ...

  5. Gold-catalyzed domino reactions.

    Science.gov (United States)

    Michelet, Véronique

    2015-01-01

    Gold-catalyzed reactions have appeared to be highly attractive tools for chemists to promote novel transformations to prepare elaborated structures from simple starting materials. This chapter presents selected and original examples of domino processes in the presence of gold catalysts, highlighting reports implying hydration, hydroxylation, and hydroamination as key starting point for cascade transformations. Domino processes implying 1,n-enynes, asymmetric domino transformations, and applications of all the presented processes in total synthesis are presented.

  6. Practical aspects and mechanism of asymmetric hydrogenation with chiral half-sandwich complexes.

    Science.gov (United States)

    Václavík, Jiří; Sot, Petr; Vilhanová, Beáta; Pecháček, Jan; Kuzma, Marek; Kačer, Petr

    2013-06-10

    This review is oriented toward the asymmetric transfer hydrogenation (ATH) of imines regarding mostly fundamental, yet important topics from the practical point of view. Development of analytical methods for the monitoring of ATH (i.e., kinetics and stereoselectivity) belongs to those topics, as well as studies on the influence of reaction conditions and structural variations on the reaction performance. The second part is devoted to the reaction mechanism with the emphasis on imine ATH and catalyst behaviour under acidic conditions. The review also addresses the asymmetric hydrogenation (AH) of ketones and imines using molecular hydrogen and the application of ATH in pharmaceutical projects. The contributions of our group to each area are included.

  7. Practical Aspects and Mechanism of Asymmetric Hydrogenation with Chiral Half-Sandwich Complexes

    Directory of Open Access Journals (Sweden)

    Petr Kačer

    2013-06-01

    Full Text Available This review is oriented toward the asymmetric transfer hydrogenation (ATH of imines regarding mostly fundamental, yet important topics from the practical point of view. Development of analytical methods for the monitoring of ATH (i.e., kinetics and stereoselectivity belongs to those topics, as well as studies on the influence of reaction conditions and structural variations on the reaction performance. The second part is devoted to the reaction mechanism with the emphasis on imine ATH and catalyst behaviour under acidic conditions. The review also addresses the asymmetric hydrogenation (AH of ketones and imines using molecular hydrogen and the application of ATH in pharmaceutical projects. The contributions of our group to each area are included.

  8. Asymmetric Bessel-Gauss beams.

    Science.gov (United States)

    Kotlyar, V V; Kovalev, A A; Skidanov, R V; Soifer, V A

    2014-09-01

    We propose a three-parameter family of asymmetric Bessel-Gauss (aBG) beams with integer and fractional orbital angular momentum (OAM). The aBG beams are described by the product of a Gaussian function by the nth-order Bessel function of the first kind of complex argument, having finite energy. The aBG beam's asymmetry degree depends on a real parameter c≥0: at c=0, the aBG beam is coincident with a conventional radially symmetric Bessel-Gauss (BG) beam; with increasing c, the aBG beam acquires a semicrescent shape, then becoming elongated along the y axis and shifting along the x axis for c≫1. In the initial plane, the intensity distribution of the aBG beams has a countable number of isolated optical nulls on the x axis, which result in optical vortices with unit topological charge and opposite signs on the different sides of the origin. As the aBG beam propagates, the vortex centers undergo a nonuniform rotation with the entire beam about the optical axis (c≫1), making a π/4 turn at the Rayleigh range and another π/4 turn after traveling the remaining distance. At different values of the c parameter, the optical nulls of the transverse intensity distribution change their position, thus changing the OAM that the beam carries. An isolated optical null on the optical axis generates an optical vortex with topological charge n. A vortex laser beam shaped as a rotating semicrescent has been generated using a spatial light modulator.

  9. A New Asymmetric α-Amido-hydroxyalkylation Mediated by SmI2

    Institute of Scientific and Technical Information of China (English)

    ZHENG Xiao; FENG Chen-Guo; HUNG Pei-Qiang

    2004-01-01

    Polyhydroxylated indolizidine alkaloids, such as castanospermine (Ⅰ) and swainsonine (H)are of longstanding interest due to their powerful glycosidase inhibitory activity. Asymmetric hydroxyatkylation via α-amido carbanions to form C-C bands would provide a convenient approach to these compounds.In continuation of our efforts in developing asyrmmetric o-amido-hydroxyalkylation method,1 we report a new SmI2 mediated flexible asymmetric α-amido-hydroxyalkylation method. Starting from the known (S)-3-hydroxy-2-pyrrolidinone 1,2 sulfide 2 and 3 were prepared. SmI2-mediated reductive metallation of these sulfides followed by reaction with ketones or aldehydes under Barbier conditions provided C2 hydroxyalkylated products 4 in yields ranged from 30% to 83%. High C2/C3 trans diastereoselectivity and mediocre diastereoselectivity at newly formed carbinolic center have been observed. The present method will open an avenue for the asymmetric synthesis of polyhydroxylated indolizidine alkaloids.

  10. Asymmetric Receptor Contact is Required for Tyrosine Autophosphorylation of Fibroblast Growth Factor Receptor in Living Cells

    Energy Technology Data Exchange (ETDEWEB)

    Bae, J.; Boggon, T; Tomé, F; Mandiyan, V; Lax, I; Schlessinge, J

    2010-01-01

    Tyrosine autophosphorylation of receptor tyrosine kinases plays a critical role in regulation of kinase activity and in recruitment and activation of intracellular signaling pathways. Autophosphorylation is mediated by a sequential and precisely ordered intermolecular (trans) reaction. In this report we present structural and biochemical experiments demonstrating that formation of an asymmetric dimer between activated FGFR1 kinase domains is required for transphosphorylation of FGFR1 in FGF-stimulated cells. Transphosphorylation is mediated by specific asymmetric contacts between the N-lobe of one kinase molecule, which serves as an active enzyme, and specific docking sites on the C-lobe of a second kinase molecule, which serves a substrate. Pathological loss-of-function mutations or oncogenic activating mutations in this interface may hinder or facilitate asymmetric dimer formation and transphosphorylation, respectively. The experiments presented in this report provide the molecular basis underlying the control of transphosphorylation of FGF receptors and other receptor tyrosine kinases.

  11. Asymmetric tandem organic solar cells

    Science.gov (United States)

    Howells, Thomas J.

    where it is used to predict the short-circuit current (Jsc) generation of the sub-cells, which is not accessible experimentally. Current-matching is then used to predict the Jsc of the complete tandem device. . As a support to the optical modelling, ellipsometry measurements of thin films of ClAlPc are presented. These films of known thickness are analysed to extract the complex refractive index for use in optical modelling calculations. A dependence of the complex refractive index on film thickness and substrate is also noted. Finally, the external quantum efficiency (EQE) technique is considered as applied to solar cells, and an additional method is proposed to characterise current balancing in asymmetric tandem cells under illumination. This technique is verified experimentally by two separate sets of data..

  12. Organocatalytic asymmetric epoxidation and tandem epoxidation/Passerini reaction under eco-friendly reaction conditions.

    Science.gov (United States)

    Deobald, Anna Maria; Corrêa, Arlene G; Rivera, Daniel G; Paixão, Márcio Weber

    2012-10-14

    An eco-friendly synthesis of highly functionalized epoxides and their incorporation into an organocatalytic multicomponent approach are reported. For this, a modified class of diarylprolinol silyl ethers was designed to enable high catalytic activity in an environmentally benign solvent system. The one-pot procedure showed great efficiency in promoting stereoselective multicomponent transformations in a tandem, 'green' fashion. Because of its non-residual, efficient and selective character, this synthetic design shows promise for large-scale applications in both diversity and target-oriented syntheses.

  13. Control of apoptosis by asymmetric cell division.

    Directory of Open Access Journals (Sweden)

    Julia Hatzold

    2008-04-01

    Full Text Available Asymmetric cell division and apoptosis (programmed cell death are two fundamental processes that are important for the development and function of multicellular organisms. We have found that the processes of asymmetric cell division and apoptosis can be functionally linked. Specifically, we show that asymmetric cell division in the nematode Caenorhabditis elegans is mediated by a pathway involving three genes, dnj-11 MIDA1, ces-2 HLF, and ces-1 Snail, that directly control the enzymatic machinery responsible for apoptosis. Interestingly, the MIDA1-like protein GlsA of the alga Volvox carteri, as well as the Snail-related proteins Snail, Escargot, and Worniu of Drosophila melanogaster, have previously been implicated in asymmetric cell division. Therefore, C. elegans dnj-11 MIDA1, ces-2 HLF, and ces-1 Snail may be components of a pathway involved in asymmetric cell division that is conserved throughout the plant and animal kingdoms. Furthermore, based on our results, we propose that this pathway directly controls the apoptotic fate in C. elegans, and possibly other animals as well.

  14. Dynamic response of the ITER tokamak during asymmetric VDEs

    Energy Technology Data Exchange (ETDEWEB)

    Schioler, Tyge, E-mail: tyge.schioler@iter.org [ITER Organization, CS 90 046, 13067 St. Paul lez Durance Cedex (France); Bachmann, Christian; Mazzone, Giuseppe; Sannazzaro, Giulio [ITER Organization, CS 90 046, 13067 St. Paul lez Durance Cedex (France)

    2011-10-15

    During the operational life of ITER, it is expected that a number of vertical displacement events (VDEs) will occur. A sub-class of these events, 'slow' asymmetric VDEs, is of particular interest from a structural point of view. This is because the forces generated during such events are both substantial and sufficiently long-lasting to significantly excite the structure. It is necessary to establish that the absolute and relative displacements of components, as well as internal and external forces, stay within acceptable limits during these events. Previous studies have investigated this problem using relatively simple models and non-rotating loads. A new, more detailed, 360-degree model was developed, and used to assess the effects of asymmetric VDEs. This paper presents the main results of this investigation. It is shown that the distance between the VV and the TFC at the inboard wall can decrease by as much as 19 mm at the equatorial plane, and that the vertical reaction force in the Vacuum Vessel supports can reach 15 MN.

  15. Asymmetric Hydrogenation of Ketones-Design of Chiral Catalysts

    Institute of Scientific and Technical Information of China (English)

    Takeshi Ohkuma

    2005-01-01

    @@ 1Introduction Asymmetric hydrogenation of ketones is one of the most reliable methods for obtaining chiral secondary alcohols. This transformation is not only of academic interest, but also of industrial significance because of its simplicity, environmental friendliness, and economic viability. Chiral RuXY(binap)(1,2-diamine) complexes (BINAP = 2,2'-bis(diphenyl-phosphino)-1, 1'-binaphthyl,X = Y = C1 or X = H, Y = BH4) with[1] or without[2] a strong base catalyze rapid, highly productive asymmetric hydrogenation of various simple ketones in 2-propanol. This reaction, unlike conventional hydrogenation, proceeds selectively at a C = O bond leaving coexisting C = C linkages intact. A range of chiral alcohols are accessible in high enantiomeric purity from aromatic,heteroaromatic, olefinic, and amino ketones by this method[1,2]. However, no universal chiral catalysts exist due to the structural diversity of ketonic substrates. Thus, tert-alkyl ketones and 1-tetralones have remained difficult to be hydrogenated with high reactivity and enantioselectivity. We here report that this problem can be resolved by the use of BINAP/PICA-Ru (PICA = α-picolylamine)[3] or BINAP/1,4-diamine-Ru[4] complexes as catalysts.

  16. Asymmetric catalysis in organic synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Reilly, S.D.; Click, D.R.; Grumbine, S.K.; Scott, B.L.; Watkins, J.G.

    1998-11-01

    This is the final report of a three-year, Laboratory Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). The goal of the project was to prepare new catalyst systems, which would perform chemical reactions in an enantioselective manner so as to produce only one of the possible optical isomers of the product molecule. The authors have investigated the use of lanthanide metals bearing both diolate and Schiff-base ligands as catalysts for the enantioselective reduction of prochiral ketones to secondary alcohols. The ligands were prepared from cheap, readily available starting materials, and their synthesis was performed in a ''modular'' manner such that tailoring of specific groups within the ligand could be carried out without repeating the entire synthetic procedure. In addition, they have developed a new ligand system for Group IV and lanthanide-based olefin polymerization catalysts. The ligand system is easily prepared from readily available starting materials and offers the opportunity to rapidly prepare a wide range of closely related ligands that differ only in their substitution patterns at an aromatic ring. When attached to a metal center, the ligand system has the potential to carry out polymerization reactions in a stereocontrolled manner.

  17. Asymmetric catalysis based on tropos ligands.

    Science.gov (United States)

    Aikawa, Kohsuke; Mikami, Koichi

    2012-11-21

    All enantiopure atropisomeric (atropos) ligands essentially require enantiomeric resolution or synthetic transformation from a chiral pool. In sharp contrast, the use of tropos (chirally flexible) ligands, which are highly modular, versatile, and easy to synthesize without enantiomeric resolution, has recently been the topic of much interest in asymmetric catalysis. Racemic catalysts bearing tropos ligands can be applied to asymmetric catalysis through enantiomeric discrimination by the addition of a chiral source, which preferentially transforms one catalyst enantiomer into a highly activated catalyst enantiomer. Additionally, racemic catalysts bearing tropos ligands can also be utilized as atropos enantiopure catalysts obtained via the control of chirality by a chiral source followed by the memory of chirality. In this feature article, our results on the asymmetric catalysis via the combination of various central metals and tropos ligands are summarized.

  18. Dc SQUIDs with asymmetric shunt resistors

    Energy Technology Data Exchange (ETDEWEB)

    Rudolph, Matthias; Nagel, Joachim; Kemmler, Matthias; Koelle, Dieter; Kleiner, Reinhold [Physikalisches Institut - Experimentalphysik II and Center for Collective Quantum Phenomena in LISAplus, Universitaet Tuebingen (Germany); Meckbach, Johannes Maximilian; Ilin, Konstantin; Siegel, Michael [Institut fuer Mikro- und Nanoelektronische Systeme, Karlsruhe Institute of Technology, Karlsruhe (Germany)

    2013-07-01

    We have investigated asymmetrically shunted Nb/Al-AlO{sub x}/Nb dc SQUIDs. Simulations based on the coupled Langevin equations predict that the optimum energy resolution ε, and thus also the noise performance of such an asymmetric SQUID, can be 3-4 times better than that of its symmetric counterpart. While keeping the total resistance R identical to a comparable symmetric SQUID with R{sup -1} = R{sub 1}{sup -1} + R{sub 2}{sup -1}, we shunted only one of the two Josephson junctions with R = R{sub 1,2}/2. Both types of SQUIDs were characterized with respect to their transport and noise properties at temperature T = 4.2 K, and we compared the experimental results with numerical simulations. Experiments yielded ε ∼ 32 ℎ for an asymmetric SQUID with an inductance L = 22 pH, whereas a comparable symmetric device achieved ε = 110 ℎ.

  19. Asymmetric synthesis II more methods and applications

    CERN Document Server

    Christmann, Mathias

    2012-01-01

    After the overwhelming success of 'Asymmetric Synthesis - The Essentials', narrating the colorful history of asymmetric synthesis, this is the second edition with latest subjects and authors. While the aim of the first edition was mainly to honor the achievements of the pioneers in asymmetric syntheses, the aim of this new edition was bringing the current developments, especially from younger colleagues, to the attention of students. The format of the book remained unchanged, i.e. short conceptual overviews by young leaders in their field including a short biography of the authors. The growing multidisciplinary research within chemistry is reflected in the selection of topics including metal catalysis, organocatalysis, physical organic chemistry, analytical chemistry, and its applications in total synthesis. The prospective reader of this book is a graduate or undergraduate student of advanced organic chemistry as well as the industrial chemist who wants to get a brief update on the current developments in th...

  20. Asymmetric transfer hydrogenation of prochiral ketone catalyzed over Fe-CS/SBA-15 catalyst

    Institute of Scientific and Technical Information of China (English)

    XUE Ping; WU Tao

    2007-01-01

    A heterogeneous chiral catalyst Fe(Ⅲ)-CS (chitosan)complex/mesoporous molecular sieve SBA-15 (Santa Barbara Amorphous) was prepared.The asymmetric transfer hydrogenations of prochiral acetophenone and 4-methyl-2-pentanone to corresponding chiral alcohols were carried out on Fe-CS/SBA-15 at atmosphere pressure using 2-propanol as hydrogen donor.Effects of Fe content in catalyst,reaction temperature,reaction time and promoter KOH concentration on the conversion of substrates and enantioselectivity were investigated.Fe-CS/SBA-15 with 2.2%mass fraction Fe exhibits considerable enantioselectivity and catalytic activity for the asymmetric transfer hydrogenations of aromatic ketone and aliphatic ketone.Under optimal reaction conditions:KOH concentration 0.03 mol/L,reaction temperature 70℃ and reaction time 4 h,enantiomer excess(ee)of (R)-1-phenylethanol and conversion of acetophenone can reach 87.4%and 27.7%,respectively.Under the above KOH concentration and reaction temperature and reaction time of 8 h,the ee of(R)-4-methyl-2-pentanol and conversion 4-methyl-2-pentanone amounted to 50.2%and 25.5%,respectively.

  1. Enantioselective Vinylogous Organocascade Reactions.

    Science.gov (United States)

    Hepburn, Hamish B; Dell'Amico, Luca; Melchiorre, Paolo

    2016-08-01

    Cascade reactions are powerful tools for rapidly assembling complex molecular architectures from readily available starting materials in a single synthetic operation. Their marriage with asymmetric organocatalysis has led to the development of novel techniques, which are now recognized as reliable strategies for the one-pot enantioselective synthesis of stereochemically dense molecules. In recent years, even more complex synthetic challenges have been addressed by applying the principle of vinylogy to the realm of organocascade catalysis. The key to the success of vinylogous organocascade reactions is the unique ability of the chiral organocatalyst to transfer reactivity to a distal position without losing control on the stereo-determining events. This approach has greatly expanded the synthetic horizons of the field by providing the possibility of forging multiple stereocenters in remote positions from the catalyst's point of action with high selectivity, while simultaneously constructing multiple new bonds. This article critically describes the developments achieved in the field of enantioselective vinylogous organocascade reactions, charting the ideas, the conceptual advances, and the milestone reactions that have been essential for reaching highly practical levels of synthetic efficiency.

  2. Asymmetric acoustic transmission in multiple frequency bands

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Hong-xiang, E-mail: jsdxshx@ujs.edu.cn [Research Center of Fluid Machinery Engineering and Technology, Jiangsu University, Zhenjiang 212013 (China); Laboratory of Modern Acoustics, Institute of Acoustics, Collaborative Innovation Center of Advanced Microstructures, Nanjing University, Nanjing 210093 (China); State Key Laboratory of Acoustics, Institute of Acoustics, Chinese Academy of Sciences, Beijing 100190 (China); Yuan, Shou-qi, E-mail: Shouqiy@ujs.edu.cn [Research Center of Fluid Machinery Engineering and Technology, Jiangsu University, Zhenjiang 212013 (China); Zhang, Shu-yi [Laboratory of Modern Acoustics, Institute of Acoustics, Collaborative Innovation Center of Advanced Microstructures, Nanjing University, Nanjing 210093 (China)

    2015-11-23

    We report both experimentally and numerically that the multi-band device of the asymmetric acoustic transmission is realized by placing two periodic gratings with different periods on both sides of two brass plates immersed in water. The asymmetric acoustic transmission can exist in four frequency bands below 1500 kHz, which arises from the interaction between various diffractions from the two gratings and Lamb modes in the brass plates immersed in water. The results indicate that the device has the advantages of multiple band, broader bandwidth, and simpler structure. Our finding should have great potential applications in ultrasonic devices.

  3. Integrated asymmetric vertical coupler pressure sensors

    Science.gov (United States)

    Kiyat, Isa; Kocabas, Askin; Akcag, Imran; Aydinli, Atilla

    2004-08-01

    Design and analysis of a novel pressure sensor based on a silicon-on-insulator asymmetric integrated vertical coupler is presented. The coupler is composed of a single mode low index waveguide and a thin silicon slab. Wavelength selective optical modulation of asymmetric vertical coupler is examined in detail. Its potential for sensing applications is highlighted as an integrated optical pressure sensor which can be realized by standard silicon micro-fabrication. Sensitivity of transmission of such couplers on refractive index change of silicon slab ensures that they are good candidates for applications requiring high sensitivities.

  4. Deep inelastic scattering on asymmetric nuclei

    Science.gov (United States)

    Saito, K.; Boros, C.; Tsushima, K.; Bissey, F.; Afnan, I. R.; Thomas, A. W.

    2000-11-01

    We study deep inelastic scattering on isospin asymmetric nuclei. In particular, the difference of the nuclear structure functions and the Gottfried sum rule for the lightest mirror nuclei, 3He and 3H, are investigated. It is found that such systems can provide significant information on charge symmetry breaking and flavor asymmetry in the nuclear medium. Furthermore, we propose a new method to extract the neutron structure function from radioactive isotopes far from the line of stability. We also discuss the flavor asymmetry in the Drell-Yan process with isospin asymmetric nuclei.

  5. Asymmetric gear rectifies random robot motion

    Science.gov (United States)

    Li, He; Zhang, H. P.

    2013-06-01

    We experimentally study the dynamics of centimetric robots and their interactions with rotary gears through inelastic collisions. Under the impacts of self-propelled robots, a gear with symmetric teeth diffuses with no preferred direction of motion. An asymmetric gear, however, rectifies random motion of nearby robots which, in return, exert a torque on the gear and drive it into unidirectional motion. Rectification efficiency increases with the degree of gear asymmetry. Our work demonstrates that asymmetric environments can be used to rectify and extract energy from random motion of macroscopic self-propelled particles.

  6. Improved DFIG Capability during Asymmetrical Grid Faults

    DEFF Research Database (Denmark)

    Zhou, Dao; Blaabjerg, Frede

    2015-01-01

    , the capability of a 2 MW DFIG to ride through asymmetrical grid faults can be estimated at the existing design of the power electronics converter. Finally, a control scheme aimed to improve the DFIG capability is proposed and the simulation results validate its feasibility.......In the wind power application, different asymmetrical types of the grid fault can be categorized after the Y/d transformer, and the positive and negative components of a single-phase fault, phase-to-phase fault, and two-phase fault can be summarized. Due to the newly introduced negative and even...

  7. Asymmetric localization in disordered Landau bands

    Energy Technology Data Exchange (ETDEWEB)

    Nita, M [Institute of Physics and Technology of Materials, PO Box MG7, Bucharest-Magurele (Romania); Aldea, A [Institute of Physics and Technology of Materials, PO Box MG7, Bucharest-Magurele (Romania); Zittartz, J [Institute of Theoretical Physics, Cologne University, 50937 Cologne (Germany)

    2007-06-06

    We show that, due to band mixing, the eigenstate localization within the disordered Landau bands gets an asymmetric structure: the degree of localization increases in the lower part of the band and decreases in the upper one. The calculation is performed for a two-dimensional lattice with the Anderson disorder potential and we prove that this effect is related to the upper shift of the extended states within the band and is enhanced by the disorder strength. The asymmetric localization and the energy shift disappear when the interband coupling is switched off.

  8. Asymmetric multiscale behavior in PM2.5 time series: Based on asymmetric MS-DFA

    Science.gov (United States)

    Zhang, Chen; Ni, Zhiwei; Ni, Liping

    2016-11-01

    Particulate matter with an aerodynamic diameter of 2.5 mm or less (PM2.5) is one of the most serious air pollution, considered most harmful for people by World Health Organisation. In this paper, we utilized the asymmetric multiscale detrended fluctuation analysis (A-MSDFA) method to explore the existence of asymmetric correlation properties for PM2.5 daily average concentration in two USA cities (Fresno and Los Angeles) and two Chinese cities (Hong Kong and Shanghai), and to assess the properties of these asymmetric correlations. The results show the existences of asymmetric correlations, and the degree of asymmetric for two USA cities is stronger than that of two Chinese cities. Further, most of the local exponent β(n) are smaller than 0.5, which indicates the existence of anti-persistent long-range correlation for PM2.5 time series in four cities. In addition, we reanalyze the asymmetric correlation by the A-MSDFA method with secant rolling windows of different sizes, which can investigate dynamic changes in the multiscale correlation for PM2.5 time series with changing window size. Whatever window sizes, the correlations are asymmetric and display smaller asymmetries at small scales and larger asymmetries at large scales. Moreover, the asymmetries become increasingly weaker with the increase of window sizes.

  9. Enantio- and periselective nitroalkene Diels-Alder reaction.

    Science.gov (United States)

    Narcis, Maurice J; Sprague, Daniel J; Captain, Burjor; Takenaka, Norito

    2012-12-14

    The periselective Diels-Alder reaction of 5-substituted pentamethylcyclopentadienes and nitroethylene has been realized by helical-chiral hydrogen bond donor catalysts. To our knowledge, this represents the first asymmetric catalytic nitroalkene Diels-Alder reaction via activation of nitroalkene, and thus establishes its proof-of-principle.

  10. Efficient copper-mediated reactions of nitrenes derived from sulfonimidamides.

    Science.gov (United States)

    Leca, Dominique; Toussaint, Aurélie; Mareau, Camille; Fensterbank, Louis; Lacôte, Emmanuel; Malacria, Max

    2004-09-30

    [reaction: see text] Sulfonimidamides lead efficiently to nitrenes and have been converted to sulfimides, sulfoximines, and aziridines in good yields, through a copper-mediated multicomponent reaction. The stereogenic sulfur atom and the trivalent nitrogen atom present in the molecules open the way to asymmetric synthesis, whose first results are presented.

  11. Ni(ii)-catalyzed asymmetric addition of arylboronic acids to cyclic imines.

    Science.gov (United States)

    Quan, Mao; Tang, Liang; Shen, Jiaqi; Yang, Guoqiang; Zhang, Wanbin

    2017-01-03

    A Ni(ii)-catalyzed asymmetric addition of arylboronic acids to cyclic aldimines and ketimines is reported. Our tropos phosphine-oxazoline biphenyl ligand is crucial for the high catalytic activity, which coordinates to Ni(ii) to form a complex with a single axial configuration. The desired chiral amine products could be prepared with excellent yields (up to 99%) and enantioselectivities (up to 99.8%) under mild reaction conditions.

  12. Asymmetric Synthesis of Optically Active Spirocyclic Indoline Scaffolds through an Enantioselective Reduction of Indoles

    KAUST Repository

    Borrmann, Ruediger

    2016-11-30

    An enantioselective synthesis of spirocyclic indoline scaffolds was achieved by applying an asymmetric iridium-catalyzed hydrogenation of 3H-indoles. Low catalyst loadings and mild reaction conditions provide a broad range of differently substituted products with excellent yields and enantioselectivities. The developed methodology allows an efficient synthesis of this important spirocyclic structural motif, which is present in numerous biologically active molecules and privileged structures in medicinal chemistry.

  13. Asymmetric total synthesis of (-)-lundurine B and determination of its absolute stereochemistry.

    Science.gov (United States)

    Nakajima, Masaya; Arai, Shigeru; Nishida, Atsushi

    2015-04-01

    A total synthesis of the Kopsia tenuis alkaloid (-)-lundurine B has been achieved. A quaternary chiral carbon has been created by an asymmetric deprotonation using a symmetric spiro cyclohexanone intermediate with a chiral lithium amide. The hexacyclic skeleton was sequentially constructed through metal-mediated reactions. The absolute stereochemistry of intermediate 5 has been unambiguously established by X-ray crystallographic analysis. This is the first description of the absolute stereochemistry of Kopsia tenuis alkaloids based on chemical synthesis.

  14. Asymmetric synthesis of propranolol, naftopidil and (R)-monobutyrin using a glycerol desymmetrization strategy

    OpenAIRE

    Lokhande,Mahendra N.; Chopade,Manojkumar U.; Bhangare,Dattatrya N.; Nikalje,Milind D.

    2013-01-01

    Herein, an approach for desymmetrization of glycerol by using a readily available camphorsulfonamide as a starting material is described. The strategy for asymmetric synthesis of (R)/(S)-propranolol, (R)/(S)-naftopidil and (R)-monobutyrin with spiroketal formation by desymmetrization was employed and Mitsunobu reaction was used for epoxide and ether formation. Steglich esterification and CAN (cerium ammonium nitrate) mediated ketal deprotection, were key steps in the synthesis. Regioselective...

  15. Asymmetric hydroformylation of Z-enamides and enol esters with rhodium-bisdiazaphos catalysts.

    Science.gov (United States)

    Abrams, M Leigh; Foarta, Floriana; Landis, Clark R

    2014-10-15

    Asymmetric hydroformylation (AHF) of Z-enamides and Z-enol esters provides chiral, alpha-functionalized aldehydes with high selectivity and atom economy. Rh-bisdiazaphospholane catalysts enable hydroformylation of these challenging disubstituted substrates under mild reaction conditions and low catalyst loadings. The synthesis of a protected analog of l-DOPA demonstrates the utility of AHF for enantioselective, atom-efficient synthesis of peptide precursors.

  16. Spatially inhomogeneous condensate in asymmetric nuclear matter

    NARCIS (Netherlands)

    Sedrakian, A

    2001-01-01

    We study the isospin singlet pairing in asymmetric nuclear matter with nonzero total momentum of the condensate Cooper pairs. The quasiparticle excitation spectrum is fourfold split compared to the usual BCS spectrum of the symmetric, homogeneous matter. A twofold splitting of the spectrum into sepa

  17. Integrated Optical Asymmetric Coupler Pressure Sensor

    Science.gov (United States)

    Kiyat, Isa; Kocabas, Coskun; Aydinli, Atilla

    2004-05-01

    Analysis of a novel pressure sensor based on a silicon-on-insulator (SOI) asymmetric vertical coupler is presented. The integrated optical component is a coupler composed of a single mode (SM) low index waveguide and a thin silicon slab. High sensitivities of about 0.14 rad.kPa-1 should be achieved.

  18. Catalytic Asymmetric Synthesis of Phosphine Boronates.

    Science.gov (United States)

    Hornillos, Valentín; Vila, Carlos; Otten, Edwin; Feringa, Ben L

    2015-06-26

    The first catalytic enantioselective synthesis of ambiphilic phosphine boronate esters is presented. The asymmetric boration of α,β-unsaturated phosphine oxides catalyzed by a copper bisphosphine complex affords optically active organoboronate esters that bear a vicinal phosphine oxide group in good yields and high enantiomeric excess. The synthetic utility of the products is demonstrated through stereospecific transformations into multifunctional optically active compounds.

  19. Beam-beam issues in asymmetric colliders

    Energy Technology Data Exchange (ETDEWEB)

    Furman, M.A.

    1992-07-01

    We discuss generic beam-beam issues for proposed asymmetric e{sup +}- e{sup -} colliders. We illustrate the issues by choosing, as examples, the proposals by Cornell University (CESR-B), KEK, and SLAC/LBL/LLNL (PEP-II).

  20. Asymmetric conditional volatility in international stock markets

    Science.gov (United States)

    Ferreira, Nuno B.; Menezes, Rui; Mendes, Diana A.

    2007-08-01

    Recent studies show that a negative shock in stock prices will generate more volatility than a positive shock of similar magnitude. The aim of this paper is to appraise the hypothesis under which the conditional mean and the conditional variance of stock returns are asymmetric functions of past information. We compare the results for the Portuguese Stock Market Index PSI 20 with six other Stock Market Indices, namely the SP 500, FTSE 100, DAX 30, CAC 40, ASE 20, and IBEX 35. In order to assess asymmetric volatility we use autoregressive conditional heteroskedasticity specifications known as TARCH and EGARCH. We also test for asymmetry after controlling for the effect of macroeconomic factors on stock market returns using TAR and M-TAR specifications within a VAR framework. Our results show that the conditional variance is an asymmetric function of past innovations raising proportionately more during market declines, a phenomenon known as the leverage effect. However, when we control for the effect of changes in macroeconomic variables, we find no significant evidence of asymmetric behaviour of the stock market returns. There are some signs that the Portuguese Stock Market tends to show somewhat less market efficiency than other markets since the effect of the shocks appear to take a longer time to dissipate.

  1. Mach bands change asymmetrically during solar eclipses.

    Science.gov (United States)

    Ross, John; Diamond, Mark R; Badcock, David R

    2003-01-01

    Observations made during two partial eclipses of the Sun show that the Mach bands on shadows cast by the Sun disappear and reappear asymmetrically as an eclipse progresses. These changes can be explained as due to changes in the shape of the penumbras of shadows as the visible portion of the Sun forms crescents of different orientation.

  2. THz operation of asymmetric-nanochannel devices

    NARCIS (Netherlands)

    Balocco, C.; Halsall, M.; Vinh, N. Q.; Song, A. M.

    2008-01-01

    The THz spectrum lies between microwaves and the mid-infrared, a region that remains largely unexplored mainly due to the bottleneck issue of lacking compact, solid state, emitters and detectors. Here, we report on a novel asymmetric-nanochannel device, known as the self-switching device, which can

  3. Asymmetric Hydrogenation of 3-Substituted Pyridinium Salts

    NARCIS (Netherlands)

    Renom-Carrasco, Marc; Gajewski, Piotr; Pignataro, Luca; de Vries, Johannes G.; Piarulli, Umberto; Gennari, Cesare; Lefort, Laurent

    2016-01-01

    The use of an equivalent amount of an organic base leads to high enantiomeric excess in the asymmetric hydrogenation of N-benzylated 3-substituted pyridinium salts into the corresponding piperidines. Indeed, in the presence of Et3N, a Rh-JosiPhos catalyst reduced a range of pyridinium salts with ee

  4. Nucleation Process in Asymmetric Nuclear Matter

    CERN Document Server

    Peres-Menezes, D

    1998-01-01

    An extended version of the non linear Walecka model, with rho mesons and eletromagnetic field is used to investigate the possibility of phase transitions in hot (warm) nuclear matter, giving rise to droplet formation. Surface properties of asymmetric nuclear matter as the droplet surface energy and its thickness are also examined.

  5. Dynamic Conditional Correlations for Asymmetric Processes

    NARCIS (Netherlands)

    M. Asai (Manabu); M.J. McAleer (Michael)

    2010-01-01

    textabstractThe paper develops two Dynamic Conditional Correlation (DCC) models, namely the Wishart DCC (WDCC) model and the Matrix-Exponential Conditional Correlation (MECC) model. The paper applies the WDCC approach to the exponential GARCH (EGARCH) and GJR models to propose asymmetric DCC models.

  6. Three dimensional force balance of asymmetric droplets

    Science.gov (United States)

    Kim, Yeseul; Lim, Su Jin; Cho, Kun; Weon, Byung Mook

    2016-11-01

    An equilibrium contact angle of a droplet is determined by a horizontal force balance among vapor, liquid, and solid, which is known as Young's law. Conventional wetting law is valid only for axis-symmetric droplets, whereas real droplets are often asymmetric. Here we show that three-dimensional geometry must be considered for a force balance for asymmetric droplets. By visualizing asymmetric droplets placed on a free-standing membrane in air with X-ray microscopy, we are able to identify that force balances in one side and in other side control pinning behaviors during evaporation of droplets. We find that X-ray microscopy is powerful for realizing the three-dimensional force balance, which would be essential in interpretation and manipulation of wetting, spreading, and drying dynamics for asymmetric droplets. This research was supported by Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education (NRF-2016R1D1A1B01007133).

  7. Dynamic Conditional Correlations for Asymmetric Processes

    NARCIS (Netherlands)

    M. Asai (Manabu); M.J. McAleer (Michael)

    2010-01-01

    textabstractThe paper develops two Dynamic Conditional Correlation (DCC) models, namely the Wishart DCC (WDCC) model and the Matrix-Exponential Conditional Correlation (MECC) model. The paper applies the WDCC approach to the exponential GARCH (EGARCH) and GJR models to propose asymmetric DCC models.

  8. Weak chaos in the asymmetric heavy top

    CERN Document Server

    Barrientos, M; Ranada, A F

    1995-01-01

    We consider the dynamics of the slightly asymmetric heavy top, a non-integrable system obtained from the Lagrange top by breaking the symmetry of its inertia tensor. It shows signs of weak chaos, which we study numerically. We argue that it is a good example for introducing students to non-integrability and chaos. (author)

  9. Asymmetric relationships between proteins shape genome evolution.

    NARCIS (Netherlands)

    Notebaart, R.A.; Kensche, P.R.; Huynen, M.A.; Dutilh, B.E.

    2009-01-01

    BACKGROUND: The relationships between proteins are often asymmetric: one protein (A) depends for its function on another protein (B), but the second protein does not depend on the first. In metabolic networks there are multiple pathways that converge into one central pathway. The enzymes in the conv

  10. Standards vs. labels with imperfect competition and asymmetric information

    DEFF Research Database (Denmark)

    Baltzer, Kenneth Thomas

    2012-01-01

    I demonstrate that providing information about product quality is not necessarily the best way to address asymmetric information problems when markets are imperfectly competitive. In a vertical differentiation model I show that a Minimum Quality Standard, which retains asymmetric information...

  11. Standards vs. labels with imperfect competition and asymmetric information

    DEFF Research Database (Denmark)

    Baltzer, Kenneth Thomas

    I demonstrate that providing information about product quality is not necessarily the best way to address asymmetric information problems when markets are imperfectly competitive. In a vertical dierentiation model I show that a Minimum Quality Standard, which retains asymmetric information...

  12. Development of a new Lewis base-tolerant chiral LBA and its application to catalytic asymmetric protonation reaction†

    OpenAIRE

    Cheon, Cheol Hong; Imahori, Tatsushi; Yamamoto, Hisashi

    2010-01-01

    A new Lewis base-tolerant LBA (Lewis Acid Assisted Brønsted Acid) derived from La(OTf)3 and (S)-HOP has been developed as a new chiral Brønsted acid. This acid has been successfully applied as a catalyst to asymmetric protonation reactions of silyl enol ethers of 2-substituted cyclic ketones.

  13. Solid-state Asymmetric Reduction of (S)-1, l'-Bi-2-naphtholAcetylferrocene Molecular Compound with Sodium Borohydride

    Institute of Scientific and Technical Information of China (English)

    MENG, Ji-Ben; DU, Hai-Feng; DING, Kui-Ling

    2001-01-01

    A novel molecular crystal formed between enanteopure 1,l'bi-2-naphthoi and acetylferrocene has been prepared andcharacterized in this communication. The examination on itsreducton with soditma borohydride showed that the asymnetric inducton was observed in the solid state but not in the solution phase. The asymmetric induction in the solid-state reaction may be attributed to the chiral microenviromnent ofmolecular crystal.

  14. (Salen)Ti(Ⅳ)-Catalyzed Asymmetric Ring-opening of meso Epoxides Using Dithiophosphorus Acid as the Nucleophile

    Institute of Scientific and Technical Information of China (English)

    Zheng Hong ZHOU; Zhao Ming LI; Bing LIU; Kang Ying LI; Li Xin WANG; Guo Feng ZHAO; Qi Lin ZHOU; Chu Chi TANG

    2006-01-01

    The asymmetric ring-opening of epoxides with dithiophosphorus acids catalyzed by a (salen)Ti(Ⅳ) complex formed in situ from the reaction of Ti(OPr-i)4 and the chiral Schiff base derived from (1R,2R)-(+)-diaminocyclohexane was realized. The resulting products were obtained with low to good enantioselectivity (up to 73% ee).

  15. Chiral dirhodium(II) carboxylates and carboxamidates as effective chemzymes in asymmetric synthesis of three-membered carbocycles.

    Science.gov (United States)

    Adly, Frady G; Ghanem, Ashraf

    2014-11-01

    In this review the recent advances in the utilization of two of the most important classes of dirhodium(II) paddlewheel complexes, dirhodium(II) carboxylates and carboxamidates, as chemzymes in inter- and intramolecular asymmetric cyclopropanation, as well as cyclopropenation reactions are discussed.

  16. A highly efficient and recoverable bi-cinchona alkaloid ligand for the catalytic asymmetric aminohydroxylation of olefins

    Directory of Open Access Journals (Sweden)

    SHENGYONG ZHANG

    2006-10-01

    Full Text Available A new freely recyclable bi-cinchona alkaloid ligand has been developed for the homogeneous catalytic asymmetric aminohydroxylation (AA of olefins. It can be easily recovered by precipitation and reused for 5 times without any significant loss in its catalytic efficiency in AA reactions.

  17. Asymmetric Bilayer Muscles: Cooperative Actuation, Dynamic Hysteresis, and Creeping in NaPF6 Aqueous Solutions.

    Science.gov (United States)

    Fuchiwaki, Masaki; Martinez, Jose G; Fernandez Otero, Toribio

    2016-08-01

    Three bilayer muscles [polypyrrole-paraphenolsulfonic acid/polypyrrole-dodecylbenzensulfonic acid (PPy-HpPS/PPy-DBS) asymmetric bilayer, PPy-HpPS/tape, and PPy-DBS/tape] were characterized during potential cycling in NaPF6 aqueous solutions. In parallel, the angular displacement of the muscle was video-recorded. The dynamo-voltammetric (angle-potential) and coulo-dynamic (charge-potential) results give the reaction-driven ionic exchanges in each PPy film. Electrochemical reactions drive the exchange of anions from the PPy-HpPS layer and cations from the PPy-DBS layer. This means that both layers from the asymmetric bilayer follow complementary volume changes (swelling/shrinking or shrinking/swelling), owing to complementary ionic exchanges (entrance/expulsion) driven by the bilayer oxidation or reduction. The result is a cooperative actuation; the bending amplitude described by the asymmetric bilayer muscle is one order of magnitude larger than those attained from each of the conducting polymer/tape muscles. The cooperative actuation almost eliminates creeping effects. A large dynamical hysteresis persists, which can be attributed to an irreversible reaction of the organic acid components at high overpotentials.

  18. 1H-Imidazol-4(5H)-ones and thiazol-4(5H)-ones as emerging pronucleophiles in asymmetric catalysis

    Science.gov (United States)

    Mielgo, Antonia

    2016-01-01

    Summary Asymmetric catalysis represents a very powerful tool for the synthesis of enantiopure compounds. In this context the main focus has been directed not only to the search for new efficient chiral catalysts, but also to the development of efficient pronucleophiles. This review highlights the utility and first examples of 1H-imidazol-4(5H)-ones and thiazol-4(5H)-ones as pronucleophiles in catalytic asymmetric reactions. PMID:27340482

  19. 1H-Imidazol-4(5H)-ones and thiazol-4(5H)-ones as emerging pronucleophiles in asymmetric catalysis.

    Science.gov (United States)

    Mielgo, Antonia; Palomo, Claudio

    2016-01-01

    Asymmetric catalysis represents a very powerful tool for the synthesis of enantiopure compounds. In this context the main focus has been directed not only to the search for new efficient chiral catalysts, but also to the development of efficient pronucleophiles. This review highlights the utility and first examples of 1H-imidazol-4(5H)-ones and thiazol-4(5H)-ones as pronucleophiles in catalytic asymmetric reactions.

  20. Ring-Contraction Strategy for the Practical, Scalable, Catalytic Asymmetric Synthesis of Versatile γ-Quaternary Acylcyclopentenes

    KAUST Repository

    Hong, Allen Y.

    2011-02-24

    Contraction action! A simple protocol for the catalytic asymmetric synthesis of highly functionalized γ-quaternary acylcyclopentenes (see schematic) in up to 91 % overall yield and 92 % ee has been developed. The reaction sequence employs a palladium-catalyzed enantioselective alkylation reaction and exploits the unusual stability of β-hydroxy cycloheptanones to achieve a general and robust method for performing two-carbon ring contractions.

  1. Organocatalyzed Asymmetric α-Oxidation, α-Aminoxylation and α-Amination of Carbonyl Compounds

    Directory of Open Access Journals (Sweden)

    Worawan Bhanthumnavin

    2010-02-01

    Full Text Available Organocatalytic asymmetric α-oxidation and amination reactions of carbonyl compounds are highly useful synthetic methodologies, especially in generating chiral building blocks that previously have not been easily accessible by traditional methods. The concept is relatively new and therefore the list of new catalysts, oxidizing and aminating reagents, as well as new substrates, are expanding at an amazing rate. The scope of this review includes new reactions and catalysts, mechanistic aspects and synthetic applications of α-oxidation, hydroxylation, aminoxylation, amination, hydrazination, hydroxyamination and related α-heteroatom functionalization of aldehydes, ketones and related active methylene compounds published during 2005–2009.

  2. Simultaneous axial screw dislocation-mediated growth and radial layer-by-layer deposition for controlled synthesis of asymmetric axial ZnO nanospindles

    Science.gov (United States)

    Yang, Hong-Jie; He, Sheng-Yan; Tuan, Hsing-Yu

    2014-07-01

    Single-component nanostructures with axial asymmetry were successfully synthesized in organic solvents via a new type of growth model. Asymmetric axial ZnO nanospindles with a hexagonal cross-section were produced by a growth model consisting of simultaneous axial screw dislocation-mediated growth and radial layer-by-layer deposition. The growth process of ZnO nanospindles is explained by comprehensively characterizing and monitoring the products at different reaction time intervals. Hexagonal discs containing dislocations were first generated at a reaction time of 2.5 min. When the reaction time continued to increase, the nanodiscs grew along the direction. Half-nanospindles were formed at mid-reaction stage when the growth rate of [0001] was greater than [000-1]. Finally, the asymmetric nanospindles were obtained at 40 min. Further, the length of the asymmetric axial ZnO spindles can be precisely tuned by the adjustment of reaction temperature. Thus, the growth model presented here can synthesize a new category of one-dimensional asymmetric nanostructures.Single-component nanostructures with axial asymmetry were successfully synthesized in organic solvents via a new type of growth model. Asymmetric axial ZnO nanospindles with a hexagonal cross-section were produced by a growth model consisting of simultaneous axial screw dislocation-mediated growth and radial layer-by-layer deposition. The growth process of ZnO nanospindles is explained by comprehensively characterizing and monitoring the products at different reaction time intervals. Hexagonal discs containing dislocations were first generated at a reaction time of 2.5 min. When the reaction time continued to increase, the nanodiscs grew along the direction. Half-nanospindles were formed at mid-reaction stage when the growth rate of [0001] was greater than [000-1]. Finally, the asymmetric nanospindles were obtained at 40 min. Further, the length of the asymmetric axial ZnO spindles can be precisely tuned by the

  3. A new entry to asymmetric platinum(IV) complexes via oxidative chlorination.

    Science.gov (United States)

    Ravera, Mauro; Gabano, Elisabetta; Pelosi, Giorgio; Fregonese, Federico; Tinello, Stefano; Osella, Domenico

    2014-09-02

    Pt(IV) complexes are usually prepared by oxidation of the corresponding Pt(II) counterparts, typically using hydrogen peroxide or chlorine. A different way to synthesize asymmetrical Pt(IV) compounds is the oxidative chlorination of Pt(II) counterparts with N-chlorosuccinimide. The reaction between cisplatin cis-[PtCl2(NH3)2], carboplatin, cis-[PtCl2(dach)] and cis-[Pt(cbdc)(dach)] (cbdc = cyclobutane-1,1'-dicarboxylato; dach = cyclohexane-1R,2R-diamine) with N-chlorosuccinimide in ethane-1,2-diol was optimized to produce the asymmetric Pt(IV) octahedral complexes [PtA2Cl(glyc)X2] (A2 = 2 NH3 or dach; glyc = 2-hydroxyethanolato; X2 = 2 Cl or cbdc) in high yield and purity. The X-ray crystal structure of the [Pt(cbdc)Cl(dach)(glyc)] complex is also reported. Moreover, the oxidation method proved to be versatile enough to produce other mixed Pt(IV) derivatives varying the reaction medium. The two trichlorido complexes easily undergo a pH-dependent hydrolysis reaction, whereas the dicarboxylato compounds are stable enough to allow further coupling reactions for drug targeting and delivery via the glyc reactive pendant. Therefore, the coupling reaction between the [Pt(cbdc)Cl(dach)(glyc)] and a model carboxylic acid, a model amine, and selectively protected amino acids is reported.

  4. Design of Asymmetric Peptide Bilayer Membranes.

    Science.gov (United States)

    Li, Sha; Mehta, Anil K; Sidorov, Anton N; Orlando, Thomas M; Jiang, Zhigang; Anthony, Neil R; Lynn, David G

    2016-03-16

    Energetic insights emerging from the structural characterization of peptide cross-β assemblies have enabled the design and construction of robust asymmetric bilayer peptide membranes. Two peptides differing only in their N-terminal residue, phosphotyrosine vs lysine, coassemble as stacks of antiparallel β-sheets with precisely patterned charged lattices stabilizing the bilayer leaflet interface. Either homogeneous or mixed leaflet composition is possible, and both create nanotubes with dense negative external and positive internal solvent exposed surfaces. Cross-seeding peptide solutions with a preassembled peptide nanotube seed leads to domains of different leaflet architecture within single nanotubes. Architectural control over these cross-β assemblies, both across the bilayer membrane and along the nanotube length, provides access to highly ordered asymmetric membranes for the further construction of functional mesoscale assemblies.

  5. Asymmetric Dark Matter Models in SO(10)

    CERN Document Server

    Nagata, Natsumi; Zheng, Jiaming

    2016-01-01

    We systematically study the possibilities for asymmetric dark matter in the context of non-supersymmetric SO(10) models of grand unification. Dark matter stability in SO(10) is guaranteed by a remnant $\\mathbb{Z}_2$ symmetry which is preserved when the intermediate scale gauge subgroup of SO(10) is broken by a ${\\bf 126}$ dimensional representation. The asymmetry in the dark matter states is directly generated through the out-of-equilibrium decay of particles around the intermediate scale, or transferred from the baryon/lepton asymmetry generated in the Standard Model sector by leptogenesis. We systematically classify possible asymmetric dark matter candidates in terms of their quantum numbers, and derive the conditions for each case that the observed dark matter density is (mostly) explained by the asymmetry of dark matter particles.

  6. Enhancing molecule fluorescence with asymmetrical plasmonic antennas.

    Science.gov (United States)

    Lu, Guowei; Liu, Jie; Zhang, Tianyue; Shen, Hongming; Perriat, Pascal; Martini, Matteo; Tillement, Olivier; Gu, Ying; He, Yingbo; Wang, Yuwei; Gong, Qihuang

    2013-07-21

    We propose and justify by the finite-difference time-domain method an efficient strategy to enhance the spontaneous emission of a fluorophore with a multi-resonance plasmonic antenna. The custom-designed asymmetrical antenna consists of two plasmonic nanoparticles with different sizes and is able to couple efficiently to free space light through multiple localized surface plasmon resonances. This design simultaneously permits a large near-field excitation near the antenna as well as a high quantum efficiency, which results in an unusual and significant enhancement of the fluorescence of a single emitter. Such an asymmetrical antenna presents intrinsic advantages over single particle or dimer based antennas made using two identical nanostructures. This promising concept can be exploited in the large domain of light-matter interaction processes involving multiple frequencies.

  7. Asymmetric dark matter models in SO(10)

    Science.gov (United States)

    Nagata, Natsumi; Olive, Keith A.; Zheng, Jiaming

    2017-02-01

    We systematically study the possibilities for asymmetric dark matter in the context of non-supersymmetric SO(10) models of grand unification. Dark matter stability in SO(10) is guaranteed by a remnant Z2 symmetry which is preserved when the intermediate scale gauge subgroup of SO(10) is broken by a {126} dimensional representation. The asymmetry in the dark matter states is directly generated through the out-of-equilibrium decay of particles around the intermediate scale, or transferred from the baryon/lepton asymmetry generated in the Standard Model sector by leptogenesis. We systematically classify possible asymmetric dark matter candidates in terms of their quantum numbers, and derive the conditions for each case that the observed dark matter density is (mostly) explained by the asymmetry of dark matter particles.

  8. Asymmetric Vesicle Instability in Extensional Flow

    Science.gov (United States)

    Spann, Andrew; Zhao, Hong; Shaqfeh, Eric

    2012-11-01

    Previous researchers have chronicled the breakup of drops in an extensional flow as they stretch into a dumbbell shape with a long thin neck. Motivated by recent experimental observations, we study an apparently similar problem with vesicles, which are deformable but incompressible membranes that conserve area and volume. First, we simulate vesicles in an unbounded uniaxial extensional flow which are given general radial perturbations from an initially stable symmetric equilibrium state. For sufficiently low reduced volume (outer viscosity) there exists a capillary number at which an asymmetric perturbation mode will grow, resulting in the formation of an asymmetric dumbbell shape with a thin connecting cylindrical bridge analogous to the shapes associated with drop breakup. Our simulations help elucidate a mechanism for this instability based on a competition between internal pressure differentials in the vesicle resulting from the membrane bending force and ambient flow. We compare and contrast this transition to the ``standard'' drop breakup transition. Funded by NSF GRFP and Stanford Graduate Fellowship.

  9. Cosmological signatures of time-asymmetric gravity

    CERN Document Server

    Cortês, Marina; Smolin, Lee

    2016-01-01

    We develop the model proposed by Cort\\^es, Gomes & Smolin, to predict cosmological signatures of time-asymmetric extensions of general relativity they proposed recently. Within this class of models the equation of motion of chiral fermions is modified by a torsion term. This term leads to a dispersion law for neutrinos that associates a new time-varying energy with each particle. We find a new neutrino contribution to the Friedmann equation resulting from the torsion term in the Ashtekar connection. In this note we explore the phenomenology of this term and observational consequences for cosmological evolution. We show that constraints on the critical energy density will ordinarily render this term unobservably small, a maximum of order $10^{-25}$ of the neutrino energy density today. However, if the time-asymmetric dark energy is tuned to cancel the cosmological constant, the torsion effect may be a dark matter candidate.

  10. Recent Advances in Substrate-Controlled Asymmetric Induction Derived from Chiral Pool α-Amino Acids for Natural Product Synthesis.

    Science.gov (United States)

    Paek, Seung-Mann; Jeong, Myeonggyo; Jo, Jeyun; Heo, Yu Mi; Han, Young Taek; Yun, Hwayoung

    2016-07-21

    Chiral pool α-amino acids have been used as powerful tools for the total synthesis of structurally diverse natural products. Some common naturally occurring α-amino acids are readily available in both enantiomerically pure forms. The applications of the chiral pool in asymmetric synthesis can be categorized prudently as chiral sources, devices, and inducers. This review specifically examines recent advances in substrate-controlled asymmetric reactions induced by the chirality of α-amino acid templates in natural product synthesis research and related areas.

  11. Novel organosoluble polyimide based on an asymmetric bis(ether amine): 3, 4'-Bis(4-aminophenoxy)-benzophenone

    Institute of Scientific and Technical Information of China (English)

    Qian Qian Bu; Shu Jiang Zhang; Hui Li; Yan Feng Li

    2012-01-01

    A new kind of asymmetrical ether diamine,3,4'-bis(4-aminophenoxy)benzophenone (BABP),was synthesized from the nucleophilic substitution reaction of 4-chloronitrobenzene and 3,4'-dihydroxybenzophenone in the presence of potassium carbonate,followed by catalytic reduction with SnCl2-6H2O and concentrated hydrochloric acid.The prepared diamine was employed in the preparation of a novel polyimide containing asymmetrical diaryl ether segments via the polycondensation of it with BTDA by a two-step method.The resulting polyimide exhibits excellent solubility,film-forming capability and high thermal resistance.

  12. New electric field in asymmetric magnetic reconnection.

    Science.gov (United States)

    Malakit, K; Shay, M A; Cassak, P A; Ruffolo, D

    2013-09-27

    We present a theory and numerical evidence for the existence of a previously unexplored in-plane electric field in collisionless asymmetric magnetic reconnection. This electric field, dubbed the "Larmor electric field," is associated with finite Larmor radius effects and is distinct from the known Hall electric field. Potentially, it could be an important indicator for the upcoming Magnetospheric Multiscale mission to locate reconnection sites as we expect it to appear on the magnetospheric side, pointing earthward, at the dayside magnetopause reconnection site.

  13. Asymmetric Information – Adverse Selection Problem

    Directory of Open Access Journals (Sweden)

    Dumitru MARIN

    2007-01-01

    Full Text Available The present paper makes an introduction in the contract theory starting with the definitions of asymmetric information and some of the problems that generate: moral hazard and adverse selection. We provide an insight of the latest empirical studies in adverse selection in different markets. An adverse selection model, based on Rothchild and Stiglitz is also present to give a perspective of the theoretical framework.

  14. Fluorous Mixture Synthesis of Asymmetric Dendrimers

    Science.gov (United States)

    Jiang, Zhong-Xing; Yu, Yihua Bruce

    2010-01-01

    A divergent fluorous mixture synthesis (FMS) of asymmetric fluorinated dendrimers has been developed. Four generations of fluorinated dendrimers with the same fluorinated moiety were prepared with high efficiency, yield and purity. Comparison of the physicochemical properties of these dendrimers provided valuable information for their application and future optimization. This strategy has not only provided a practical method for the synthesis and purification of dendrimers, but also established the possibility of utilizing the same fluorinated moiety for FMS. PMID:20170088

  15. The Asymmetric Exclusion Process and Brownian Excursions

    Science.gov (United States)

    Derrida, B.; Enaud, C.; Lebowitz, J. L.

    2004-04-01

    We consider the totally asymmetric exclusion process (TASEP) in one dimension in its maximal current phase. We show, by an exact calculation, that the non-Gaussian part of the fluctuations of density can be described in terms of the statistical properties of a Brownian excursion. Numerical simulations indicate that the description in terms of a Brownian excursion remains valid for more general one dimensional driven systems in their maximal current phase.

  16. Temporal association in asymmetric neural networks

    Science.gov (United States)

    Sompolinsky, H.; Kanter, I.

    1986-12-01

    A neural network model which is capable of recalling time sequences and cycles of patterns is introduced. In this model, some of the synaptic connections, Jij, between pairs of neurons are asymmetric (Jij≠Jji) and have slow dynamic response. The effects of thermal noise on the generated sequences are discussed. Simulation results demonstrating the performance of the network are presented. The model may be also useful in understanding the generation of rhythmic patterns in biological motor systems.

  17. Asymmetric k-Center with Minimum Coverage

    DEFF Research Database (Denmark)

    Gørtz, Inge Li

    2008-01-01

    In this paper we give approximation algorithms and inapproximability results for various asymmetric k-center with minimum coverage problems. In the k-center with minimum coverage problem, each center is required to serve a minimum number of clients. These problems have been studied by Lim et al. [A....... Lim, B. Rodrigues, F. Wang, Z. Xu, k-center problems with minimum coverage, Theoret. Comput. Sci. 332 (1–3) (2005) 1–17] in the symmetric setting....

  18. Venture Capital Contracting Under Asymmetric Information

    OpenAIRE

    Jeffrey Trester

    1993-01-01

    The author develops a model of venture capital contracting in which the entrepreneur and venture capitalist contract under symmetric information. A condition of asymmetric information may arise subsequent to the first contract. The author shows that this condition makes debt contracts infeasible and leads to the use of preferred equity contracts. The author notes that discussions of the relation between venture capital and capital structure are rare. This paper expands the literature by addre...

  19. Asymmetric Attention: Visualizing the Uncertain Threat

    Science.gov (United States)

    2010-03-01

    this is the multiplayer online role-playing game called, “Asymmetric Warfare Virtual Training Technology ” or AW- VTT (Peck, 2005). This simulation...Personnel, Performance 622785A790 and Training Technology Approved for public release; distribution is unlimited. iii ACKNOWLEDGEMENTS I...advanced detection technologies . However, Soldiers may not utilize these resources for various reasons (Cohen, April 2009), including: no immediate or

  20. Superheavy fragments produced in the asymmetric strongly damped collision

    Institute of Scientific and Technical Information of China (English)

    TIAN Jun-Long; WU Xi-Zhen; LI Zhu-Xia; ZHAO Kai

    2008-01-01

    The strongly damped collisions of very heavy nuclei 232Th+250Cf at the energy range of 680-1880 MeV have been studied within the improved quantum molecular dynamics model. The production probability of primary superheavy fragments with Z ≥ 114 (SHFs) for the asymmetric reaction 232Th+250Cf is higher than that for the symmetric reaction 244Pu+244Pu and 238U+238U. The calculated results show that the mass and charge distributions of primary fragments, the excitation energy distribution of SHFs depend on the incident energies strongly. Two stages of the decay process of composite systems are distinguished by very different decay slopes, which imply different decay mechanisms of the composite system. The first stage is for the decay of giant composite systems and the second one corresponds to the decay of fragments of giant composite systems including SHFs through emitting neutron, proton or other charged particles, and also through fission or fragmentation. The slow reduction of SHFs in the second stage seems to be helpful for the survival of primary superheavy fragments.

  1. The dynamics and control of large flexible asymmetric spacecraft

    Science.gov (United States)

    Humphries, T. T.

    1991-02-01

    This thesis develops the equations of motion for a large flexible asymmetric Earth observation satellite and finds the characteristics of its motion under the influence of control forces. The mathematical model of the structure is produced using analytical methods. The equations of motion are formed using an expanded momentum technique which accounts for translational motion of the spacecraft hub and employs orthogonality relations between appendage and vehicle modes. The controllability and observability conditions of the full spacecraft motions using force and torque actuators are defined. A three axis reaction wheel control system is implemented for both slewing the spacecraft and controlling its resulting motions. From minor slew results it is shown that the lowest frequency elastic mode of the spacecraft is more important than higher frequency modes, when considering the effects of elastic motion on instrument pointing from the hub. Minor slews of the spacecraft configurations considered produce elastic deflections resulting in rotational attitude motions large enough to contravene pointing accuracy requirements of instruments aboard the spacecraft hub. Active vibration damping is required to reduce these hub motions to acceptable bounds in sufficiently small time. A comparison between hub mounted collocated and hub/appendage mounted non-collocated control systems verifies that provided the non-collocated system is stable, it can more effectively damp elastic modes whilst maintaining adequate damping of rigid modes. Analysis undertaken shows that the reaction wheel controller could be replaced by a thruster control system which decouples the modes of the spacecraft motion, enabling them to be individually damped.

  2. Asymmetric dimethylarginine: A novel biomarker of gastric mucosal injury?

    Institute of Scientific and Technical Information of China (English)

    Zhe Zhang; Yi-You Zou; Fu-Jun Li; Chang-Ping Hu

    2011-01-01

    Nitric oxide (NO),a multifunctional endogenous gas molecule,is metabolized from L-arginine by enzymatic reaction in the presence of nitric oxide synthase. NO,an important gas signaling molecule,is a gastric mucosa protective factor that contributes significantly to maintain normal gastric mucosa integrity. NO increases gastric mucosa blood flow,regulates the secretion of mucus and bicarbonate,and inhibits the secretion of gastric juice. Asymmetric dimethylarginine (ADMA) has been identified as the major endogenous inhibitor of nitric oxide synthase. The function of ADMA is to decrease NO production via inhibiting nitric oxide synthase activity. Besides inhibiting NO synthesis,ADMA also directly induces oxidative stress and cell apoptosis,and participates in inflammation reaction. Its systemic accumulation was observed in conjunction with several cardiovascular and metabolic diseases. ADMA also mediates gastric ulcer injury induced by ethanol,stress,helicobacter pylori and indomethacin. The mechanism of ADMA directly producing adverse effect in gastric mucosa is incompletely understood. It is widely accepted that NO bioavailability decrease is the majority reason. Promotion of apoptosis and aggravation of inflammation may be other important mechanisms of ADMA-induced gastric injury. ADMA might be a novel clinical and experimental biomarker related to gastric mucosa disorder. Although therapeutic tool targeting to ADMA is available in multiple cardiovascular diseases,it is unknown in gastrointestinal disease. The strategy to inhibit ADMA is beneficial to gastric ulcer induced by ethanol in rats. Thus,ADMA might be a candidate of therapeutic target in gastric mucosa damage.

  3. Hadron scattering in an asymmetric box*

    Science.gov (United States)

    China Lattice QCD Collaboration; Li, Xin; Chen, Ying; Meng, Guo-Zhan; Feng, Xu; Gong, Ming; He, Song; Li, Gang; Liu, Chuan; Liu, Yu-Bin; Ma, Jian-Ping; Meng, Xiang-Fei; Shen, Yan; Zhang, Jian-Bo

    2007-06-01

    We propose to study hadron-hadron scattering using lattice QCD in an asymmetric box which allows one to access more non-degenerate low-momentum modes for a given volume. The conventional Lüscher's formula applicable in a symmetric box is modified accordingly. To illustrate the feasibility of this approach, pion-pion elastic scattering phase shifts in the I = 2, J = 0 channel are calculated within quenched approximation using improved gauge and Wilson fermion actions on anisotropic lattices in an asymmetric box. After the chiral and continuum extrapolation, we find that our quenched results for the scattering phase shifts in this channel are consistent with the experimental data when the three-momentum of the pion is below 300MeV. Agreement is also found when compared with previous theoretical results from lattice and other means. Moreover, with the usage of asymmetric volume, we are able to compute the scattering phases in the low-momentum range (pion three momentum less than about 350MeV in the center of mass frame) for over a dozen values of the pion three-momenta, much more than using the conventional symmetric box with comparable volume.

  4. Asymmetric Conditional Volatility in International Stock Markets

    CERN Document Server

    Ferreira, N B; Menezes, R; Ferreira, Nuno B.; Mendes, Diana A.; Menezes, Rui

    2006-01-01

    Recent studies show that a negative shock in stock prices will generate more volatility than a positive shock of similar magnitude. The aim of this paper is to appraise the hypothesis under which the conditional mean and the conditional variance of stock returns are asymmetric functions of past information. We compare the results for the Portuguese Stock Market Index PSI 20 with six other Stock Market Indices, namely the S&P 500, FTSE100, DAX 30, CAC 40, ASE 20, and IBEX 35. In order to assess asymmetric volatility we use autoregressive conditional heteroskedasticity specifications known as TARCH and EGARCH. We also test for asymmetry after controlling for the effect of macroeconomic factors on stock market returns using TAR and M-TAR specifications within a VAR framework. Our results show that the conditional variance is an asymmetric function of past innovations raising proportionately more during market declines, a phenomenon known as the leverage effect. However, when we control for the effect of chan...

  5. Multiple Traveling Salesmen in Asymmetric Metrics

    CERN Document Server

    Friggstad, Zachary

    2011-01-01

    We consider some generalizations of the Asymmetric Traveling Salesman Path problem. Suppose we have an asymmetric metric G = (V,A) with two distinguished nodes s,t. We are also given a positive integer k. The goal is to find k paths of minimum total cost from s to t whose union spans all nodes. We call this the k-Person Asymmetric Traveling Salesmen Path problem (k-ATSPP). Our main result for k-ATSPP is a bicriteria approximation that, for some parameter b >= 1 we may choose, finds between k and k + k/b paths of total length O(b log |V|) times the optimum value of an LP relaxation based on the Held-Karp relaxation for the Traveling Salesman problem. On one extreme this is an O(log |V|)-approximation that uses up to 2k paths and on the other it is an O(k log |V|)-approximation that uses exactly k paths. Next, we consider the case where we have k pairs of nodes (s_1,t_1), ..., (s_k,t_k). The goal is to find an s_i-t_i path for every pair such that each node of G lies on at least one of these paths. Simple appro...

  6. SPECT using asymmetric pinholes with truncated projections

    Energy Technology Data Exchange (ETDEWEB)

    Lin Jianyu; Meikle, Steven R, E-mail: jianyu.lin@curtin.edu.au [Ramaciotti Imaging Centre, Brain and Mind Research Institute, University of Sydney (Australia)

    2011-07-07

    Tomographic systems employing truncated projections have been developed for parallel and fan beam collimation and for cone beam CT but the idea has not been extensively explored in pinhole single photon emission computed tomography (SPECT). In this paper, we explore the sampling requirements and system performance of SPECT systems with asymmetric pinhole collimators and truncated projections. We demonstrate that complete 3D sampling can be achieved by using multiple detectors with truncated asymmetric pinholes, offset axially from each other, and a spiral orbit. The use of truncated projections can be exploited in the design of pinhole SPECT systems by moving the pinholes closer to the subject, resulting in increased sensitivity and improved spatial resolution. Truncated and untruncated pinhole systems were evaluated using the contrast-to-noise ratio (CNR) calculated from the linearized local impulse response as a figure of merit. The CNR for the truncated pinhole system was up to 60% greater than that for the untruncated system at matched resolution for a source voxel near the centre of a uniform phantom and 30% greater at the edge. We conclude that an object can be reconstructed from asymmetric pinholes with truncated projections, which leads to potentially important design considerations and applications in single- and multi-pinhole SPECT.

  7. Traceless Synthesis of Asymmetrically Modified Bivalent Nucleosomes.

    Science.gov (United States)

    Lechner, Carolin C; Agashe, Ninad D; Fierz, Beat

    2016-02-18

    Nucleosomes carry extensive post-translational modifications (PTMs), which results in complex modification patterns that are involved in epigenetic signaling. Although two copies of each histone coexist in a nucleosome, they may not carry the same PTMs and are often differently modified (asymmetric). In bivalent domains, a chromatin signature prevalent in embryonic stem cells (ESCs), namely H3 methylated at lysine 4 (H3K4me3), coexists with H3K27me3 in asymmetric nucleosomes. We report a general, modular, and traceless method for producing asymmetrically modified nucleosomes. We further show that in bivalent nucleosomes, H3K4me3 inhibits the activity of the H3K27-specific lysine methyltransferase (KMT) polycomb repressive complex 2 (PRC2) solely on the same histone tail, whereas H3K27me3 stimulates PRC2 activity across tails, thereby partially overriding the H3K4me3-mediated repressive effect. To maintain bivalent domains in ESCs, PRC2 activity must thus be locally restricted or reversed.

  8. Asymmetric threat data mining and knowledge discovery

    Science.gov (United States)

    Gilmore, John F.; Pagels, Michael A.; Palk, Justin

    2001-03-01

    Asymmetric threats differ from the conventional force-on- force military encounters that the Defense Department has historically been trained to engage. Terrorism by its nature is now an operational activity that is neither easily detected or countered as its very existence depends on small covert attacks exploiting the element of surprise. But terrorism does have defined forms, motivations, tactics and organizational structure. Exploiting a terrorism taxonomy provides the opportunity to discover and assess knowledge of terrorist operations. This paper describes the Asymmetric Threat Terrorist Assessment, Countering, and Knowledge (ATTACK) system. ATTACK has been developed to (a) data mine open source intelligence (OSINT) information from web-based newspaper sources, video news web casts, and actual terrorist web sites, (b) evaluate this information against a terrorism taxonomy, (c) exploit country/region specific social, economic, political, and religious knowledge, and (d) discover and predict potential terrorist activities and association links. Details of the asymmetric threat structure and the ATTACK system architecture are presented with results of an actual terrorist data mining and knowledge discovery test case shown.

  9. Chiral alkynylcarbinols from marine sponges: asymmetric synthesis and biological relevance.

    Science.gov (United States)

    Listunov, Dymytrii; Maraval, Valérie; Chauvin, Remi; Génisson, Yves

    2015-01-01

    Covering: up to March 2014. Previous review on the topic: B. W. Gung, C. R. Chim., 2009, 12, 489-505. Chiral α-functional lipidic propargylic alcohols extracted from marine sponges, in particular of the pacific genus Petrosia, constitute a class of acetylenic natural products exhibiting remarkable in vitro biological activities, especially anti-tumoral cytotoxicity. These properties, associated to functionalities that are uncommon among natural products, have prompted recent projects on asymmetric total synthesis. On the basis of a three-sector structural typology, three main sub-types of secondary alkynylcarbinols (with either alkyl, alkenyl, or alkynyl as the second substituent) can be identified as the minimal pharmacophoric units. Selected natural products containing these functionalities have been targeted using previously known or on purpose-designed procedures, where the stereo-determining step can be: (i) a C-C bond forming reaction (e.g. the Zn-mediated addition of alkynyl nucleophiles to aldehydes in the presence of chiral aminoalcohols), (ii) a functional layout (e.g. the asymmetric organo- or metallo-catalytic reduction of ynones), or (iii) an enantiomeric resolution (e.g. a lipase-mediated kinetic resolution via acetylation). The promising medicinal importance of these targets is finally surveyed, and future investigation prospects are proposed, such as: (i) further total synthesis of known or future extraction products; (ii) the synthesis of non-natural analogues, with simpler lipophilic environments of the alkynylcarbinol-based pharmacophoric units; (iii) the variation and optimization of both the pharmacophoric units and their lipophilic environment; and (iv) investigations into the biological mode of action of these unique structures.

  10. Asymmetric distribution of histones during Drosophila male germline stem cell asymmetric divisions.

    Science.gov (United States)

    Tran, Vuong; Feng, Lijuan; Chen, Xin

    2013-05-01

    It has long been known that epigenetic changes are inheritable. However, except for DNA methylation, little is known about the molecular mechanisms of epigenetic inheritance. Many types of stem cells undergo asymmetric cell divisions to generate self-renewed stem cells and daughter cells committed for differentiation. Still, whether and how stem cells retain their epigenetic memory remain questions to be elucidated. During the asymmetric division of Drosophila male germline stem cell (GSC), our recent studies revealed that the preexisting histone 3 (H3) are selectively segregated to the GSC, whereas newly synthesized H3 deposited during DNA replication are enriched in the differentiating daughter cell. We propose a two-step model to explain this asymmetric histone distribution. First, prior to mitosis, preexisting histones and newly synthesized histones are differentially distributed at two sets of sister chromatids. Next, during mitosis, the set of sister chromatids that mainly consist of preexisting histones are segregated to GSCs, while the other set of sister chromatids enriched with newly synthesized histones are partitioned to the daughter cell committed for differentiation. In this review, we apply current knowledge about epigenetic inheritance and asymmetric cell division to inform our discussion of potential molecular mechanisms and the cellular basis underlying this asymmetric histone distribution pattern. We will also discuss whether this phenomenon contributes to the maintenance of stem cell identity and resetting chromatin structure in the other daughter cell for differentiation.

  11. Copper-Catalyzed SN2'-Selective Allylic Substitution Reaction of gem-Diborylalkanes.

    Science.gov (United States)

    Zhang, Zhen-Qi; Zhang, Ben; Lu, Xi; Liu, Jing-Hui; Lu, Xiao-Yu; Xiao, Bin; Fu, Yao

    2016-03-04

    A Cu/(NHC)-catalyzed SN2'-selective substitution reaction of allylic electrophiles with gem-diborylalkanes is reported. Different substituted gem-diborylalkanes and allylic electrophiles can be employed in this reaction, and various synthetic valuable functional groups can be tolerated. The asymmetric version of this reaction was initially researched with chiral N-heterocyclic carbene (NHC) ligands.

  12. Rh(I)–Bisphosphine-Catalyzed Asymmetric, Intermolecular Hydroheteroarylation of α-Substituted Acrylate Derivatives

    Science.gov (United States)

    2015-01-01

    Asymmetric hydroheteroarylation of alkenes represents a convenient entry to elaborated heterocyclic motifs. While chiral acids are known to mediate asymmetric addition of electron-rich heteroarenes to Michael acceptors, very few methods exploit transition metals to catalyze alkylation of heterocycles with olefins via a C–H activation, migratory insertion sequence. Herein, we describe the development of an asymmetric, intermolecular hydroheteroarylation reaction of α-substituted acrylates with benzoxazoles. The reaction provides 2-substitued benzoxazoles in moderate to excellent yields and good to excellent enantioselectivities. Notably, a series of mechanistic studies appears to contradict a pathway involving enantioselective protonation of a Rh(I)–enolate, despite the fact that such a mechanism is invoked almost unanimously in the related addition of aryl boronic acids to methacrylate derivatives. Evidence suggests instead that migratory insertion or beta-hydride elimination is enantiodetermining and that isomerization of a Rh(I)–enolate to a Rh(I)–heterobenzyl species insulates the resultant α-stereocenter from epimerization. A bulky ligand, CTH-(R)-Xylyl-P-Phos, is crucial for reactivity and enantioselectivity, as it likely discourages undesired ligation of benzoxazole substrates or intermediates to on- or off-cycle rhodium complexes and attenuates coordination-promoted product epimerization. PMID:25545834

  13. Asymmetric Catalysis with CO2 : The Direct α-Allylation of Ketones.

    Science.gov (United States)

    Pupo, Gabriele; Properzi, Roberta; List, Benjamin

    2016-05-10

    Quaternary stereocenters are found in numerous bioactive molecules. The Tsuji-Trost reaction has proven to be a powerful C-C bond forming process, and, at least in principle, should be well suited to access quaternary stereocenters via the α-allylation of ketones. However, while indirect approaches are known, the direct, catalytic asymmetric α-allylation of branched ketones has been elusive until today. By combining "enol catalysis" with the use of CO2 as a formal catalyst for asymmetric catalysis, we have now developed a solution to this problem: we report a direct, highly enantioselective and highly atom-economic Tsuji-Trost allylation of branched ketones with allylic alcohol. Our reaction delivers products bearing quaternary stereocenters with high enantioselectivity and water as the sole by-product. We expect our methodology to be of utility in asymmetric catalysis and inspire the design of other highly atom-economic transformations. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Charge Asymmetric Cosmic Rays as a probe of Flavor Violating Asymmetric Dark Matter

    DEFF Research Database (Denmark)

    Masina, Isabella; Sannino, Francesco

    2011-01-01

    The recently introduced cosmic sum rules combine the data from PAMELA and Fermi-LAT cosmic ray experiments in a way that permits to neatly investigate whether the experimentally observed lepton excesses violate charge symmetry. One can in a simple way determine universal properties of the unknown...... flavor violation and asymmetric dark matter are both required to have a charge asymmetry in the cosmic ray lepton excesses. Therefore, an experimental evidence of charge asymmetry in the cosmic ray lepton excesses implies that dark matter is asymmetric....

  15. A carbon nanotube confinement strategy to implement homogeneous asymmetric catalysis in the solid phase.

    Science.gov (United States)

    Hashimoto, Kazuki; Kumagai, Naoya; Shibasaki, Masakatsu

    2015-03-09

    A readily recyclable asymmetric catalyst has been developed based on the self-assembly of a homogeneous catalyst in a fibrous network of multiwalled carbon nanotubes (MWNTs). Dimerization of an amide-based chiral ligand with a suitable spacer allows for the efficient formation of a heterogeneous catalyst by self-assembly on addition of Er(OiPr)3. The self-assembly proceeds in the MWNT fibrous network and small clusters of assembled catalyst are confined in the MWNTs, producing an easily handled solid-phase catalyst. The resulting MWNT-confined catalyst exhibits a good catalytic performance in a catalytic asymmetric Mannich-type reaction, which can be conducted in a repeated batch system and in a continuous-flow platform.

  16. Asymmetric Anion-π Catalysis: Enamine Addition to Nitroolefins on π-Acidic Surfaces.

    Science.gov (United States)

    Zhao, Yingjie; Cotelle, Yoann; Avestro, Alyssa-Jennifer; Sakai, Naomi; Matile, Stefan

    2015-09-16

    Here we provide experimental evidence for anion-π catalysis of enamine chemistry and for asymmetric anion-π catalysis. A proline for enamine formation on one side and a glutamic acid for nitronate protonation on the other side are placed to make the enamine addition to nitroolefins occur on the aromatic surface of π-acidic naphthalenediimides. With increasing π acidity of the formally trifunctional catalysts, rate and enantioselectivity of the reaction increase. Mismatched and more flexible controls reveal that the importance of rigidified, precisely sculpted architectures increases with increasing π acidity as well. The absolute configuration of stereogenic sulfoxide acceptors at the edge of the π-acidic surface has a profound influence on asymmetric anion-π catalysis and, if perfectly matched, affords the highest enantio- and diastereoselectivity.

  17. Asymmetric counteranion-directed Lewis acid organocatalysis for the scalable cyanosilylation of aldehydes

    Science.gov (United States)

    Zhang, Zhipeng; Bae, Han Yong; Guin, Joyram; Rabalakos, Constantinos; van Gemmeren, Manuel; Leutzsch, Markus; Klussmann, Martin; List, Benjamin

    2016-08-01

    Due to the high versatility of chiral cyanohydrins, the catalytic asymmetric cyanation reaction of carbonyl compounds has attracted widespread interest. However, efficient protocols that function at a preparative scale with low catalyst loading are still rare. Here, asymmetric counteranion-directed Lewis acid organocatalysis proves to be remarkably successful in addressing this problem and enabled a molar-scale cyanosilylation in quantitative yield and with excellent enantioselectivity. Also, the catalyst loading could be lowered to a part-per-million level (50 ppm: 0.005 mol%). A readily accessible chiral disulfonimide was used, which in combination with trimethylsilyl cyanide, turned into the active silylium Lewis acid organocatalyst. The nature of a peculiar phenomenon referred to as a ``dormant period'', which is mainly induced by water, was systematically investigated by means of in situ Fourier transform infrared analysis.

  18. Critical phenomena of asymmetric nuclear matter in the extended Zimanyi-Moszkowski model

    CERN Document Server

    Miyazaki, K

    2005-01-01

    We have studied the liquid-gas phase transition of warm asymmetric nuclear matter in the extended Zimanyi-Moszkowski model. The three sets of the isovector-meson coupling constants are used. It is found that the critical temperature depends only on the difference of the symmetry energy but not on the differences of each isovector coupling constant. We treat the asymmetric nuclear matter as one-component system and employ the Maxwell construction so as to calculate the liquid-gas phase coexistence curve. The derived critical exponents depend on neither the symmetry energy nor the asymmetry of the system. Their values beta=0.33 and gamma=1.21 agree with the empirical values derived from the recent multifragmentation reactions. Consequently, we have confirmed the universality of the critical phenomena in the liquid-gas phase transition of nuclear matter.

  19. Catalytic asymmetric synthesis of enantioenriched heterocycles bearing a C-CF3 stereogenic center.

    Science.gov (United States)

    Huang, Yi-Yong; Yang, Xing; Chen, Zhuo; Verpoort, Francis; Shibata, Norio

    2015-06-08

    Given the important agricultural and medicinal application of optically pure heterocycles bearing a trifluoromethyl group at the stereogenic carbon center in the heterocyclic framework, the exploration of efficient and practical synthetic strategies to such types of molecules remains highly desirable. Catalytic enantioselective synthesis has one clear advantage that it is more cost-effective than other synthetic methods, but remains limited by challenges in achieving excellent yield and stereoselectivities with a low catalyst loading. Thus far, numerous models of organo- and organometal-catalyzed asymmetric reactions have been exploited to achieve this elusive goal over the past decade. This review article describes recent progress on this research topic, and focuses on an understanding of the catalytic asymmetric protocols exemplified in the catalytic enantioselective synthesis of a wide range of complex enantioenriched trifluoromethylated heterocycles.

  20. Computational Design of Intrinsic Molecular Rectifiers Based on Asymmetric Functionalization of N-Phenylbenzamide.

    Science.gov (United States)

    Ding, Wendu; Koepf, Matthieu; Koenigsmann, Christopher; Batra, Arunabh; Venkataraman, Latha; Negre, Christian F A; Brudvig, Gary W; Crabtree, Robert H; Schmuttenmaer, Charles A; Batista, Victor S

    2015-12-01

    We report a systematic computational search of molecular frameworks for intrinsic rectification of electron transport. The screening of molecular rectifiers includes 52 molecules and conformers spanning over 9 series of structural motifs. N-Phenylbenzamide is found to be a promising framework with both suitable conductance and rectification properties. A targeted screening performed on 30 additional derivatives and conformers of N-phenylbenzamide yielded enhanced rectification based on asymmetric functionalization. We demonstrate that electron-donating substituent groups that maintain an asymmetric distribution of charge in the dominant transport channel (e.g., HOMO) enhance rectification by raising the channel closer to the Fermi level. These findings are particularly valuable for the design of molecular assemblies that could ensure directionality of electron transport in a wide range of applications, from molecular electronics to catalytic reactions.

  1. Facile synthesis of a melt-spinnable polyborazine from asymmetric alkylaminoborazine

    Institute of Scientific and Technical Information of China (English)

    Yong Peng Lei; Ying De Wang; Yong Cai Song; Yi He Li; Hao Wang; Cheng Deng; Zheng Fang Xie

    2010-01-01

    A novel asymmetric alkylaminoborazine monomer,2-propylamino-4,6-bis(methylamino)borazine,was synthesized for the first time,and directly polymerized to give a melt-spinnable polyborazine(PBN).This asymmetric alkylaminoborazine was synthesized by an aminolysis reaction of 2,4,6-trichloroborazine(TCB)with different amines under mild conditions.This route turns out to be much cheaper and simpler than the conventional routes.The chemical composition,structure,molecular weights and ceramic yield were investigated by EA,FTIR,NMR,GPC and TG analysis.The PBN exhibits suitable rheological property for melt-spinning,which suggests that it is a potential precursor for BN fibers.

  2. Reaction Graph

    Institute of Scientific and Technical Information of China (English)

    傅育熙

    1998-01-01

    The paper proposes reaction graphs as graphical representations of computational objects.A reaction graph is a directed graph with all its arrows and some of its nodes labeled.Computations are modled by graph rewriting of a simple nature.The basic rewriting rules embody the essence of both the communications among processes and cut-eliminations in proofs.Calculi of graphs are ideentified to give a formal and algebraic account of reaction graphs in the spirit of process algebra.With the help of the calculi,it is demonstrated that reaction graphs capture many interesting aspects of computations.

  3. Asymmetric-Structure Analysis of Carbon and Energy Markets

    Science.gov (United States)

    Xu, Wei; Cao, Guangxi

    2016-02-01

    This study aimed to investigate the asymmetric structure between the carbon and energy markets from two aspects of different trends (up or down) and volatility-transmission direction using asymmetric detrended cross-correlation analysis (DCCA) cross-correlation coefficient test, multifractal asymmetric DCCA (MF-ADCCA) method, asymmetric volatility-constrained correlation metric and time rate of information-flow approach. We sampled 1283 observations from January 2008 to December 2012 among pairs of carbon and energy markets for analysis. Empirical results show that the (1) asymmetric characteristic from the cross-correlation between carbon and returns in the energy markets is significant, (2) asymmetric cross-correlation between carbon and energy market price returns is persistent and multifractral and (3) volatility of the base assets of energy market returns is more influential to the base asset of the carbon market than that of the energy market.

  4. L-Proline catalyzed aldol reactions between acetone and aldehydes in supercritical fluids:An environmentally friendly reaction procedure

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    The direct asymmetric aldol reaction between various aldehydes and acetone catalyzed by L-proline catalyst was successfully carried out in supercritical CO2 (scCO2) and 1,1,1,2-tetrafluoroethane (R-134a) fluids.The enantioselectivity of 84% ee to the targeted product was achieved under 20 MPa,40 °C,and 15 mol% of the catalyst in supercritical CO2 (scCO2) fluid.The effects of reaction parameters,such as temperature,pressure,catalyst loading and different substituted aldehydes on both enantioselectivity and aldol yield were discussed.The titled reaction was also performed in 1,1,1,2-tetrafluoroethane,and the obtained results were compared with those in scCO2.This new reaction procedure provides an environmental asymmetric aldol reaction system as compared with that in organic solvents.

  5. Infinite dimensional mixed economies with asymmetric information

    CERN Document Server

    Bhowmik, Anuj

    2011-01-01

    In this paper, we study asymmetric information economies consisting of both non-negligible and negligible agents and having ordered Banach spaces as their commodity spaces. In answering a question of Herv\\'{e}s-Beloso and Moreno-Garc\\'{i}a, we establish a characterization of Walrasian expectations allocations by the veto power of the grand coalition. It is also shown that when an economy contains only negligible agents a Vind's type theorem on the private core with the exact feasibility can be restored. This solves a problem of Pesce.

  6. RHIC operation with asymmetric collisions in 2015

    Energy Technology Data Exchange (ETDEWEB)

    Liu, C. [Brookhaven National Lab. (BNL), Upton, NY (United States); Aschenauer, C. [Brookhaven National Lab. (BNL), Upton, NY (United States); Atoian, G. [Brookhaven National Lab. (BNL), Upton, NY (United States); Blaskiewicz, M. [Brookhaven National Lab. (BNL), Upton, NY (United States); Brown, K. A. [Brookhaven National Lab. (BNL), Upton, NY (United States); Bruno, D. [Brookhaven National Lab. (BNL), Upton, NY (United States); Connolly, R. [Brookhaven National Lab. (BNL), Upton, NY (United States); Ottavio, T. D. [Brookhaven National Lab. (BNL), Upton, NY (United States); Drees, K. A. [Brookhaven National Lab. (BNL), Upton, NY (United States); Fischer, W. [Brookhaven National Lab. (BNL), Upton, NY (United States); Gardner, C. J. [Brookhaven National Lab. (BNL), Upton, NY (United States); Gu, X. [Brookhaven National Lab. (BNL), Upton, NY (United States); Hayes, T. [Brookhaven National Lab. (BNL), Upton, NY (United States); Huang, H. [Brookhaven National Lab. (BNL), Upton, NY (United States); Laster, J. S. [Brookhaven National Lab. (BNL), Upton, NY (United States); Luo, Y. [Brookhaven National Lab. (BNL), Upton, NY (United States); Makdisi, Y. [Brookhaven National Lab. (BNL), Upton, NY (United States); Marr, G. [Brookhaven National Lab. (BNL), Upton, NY (United States); Marusic, A. [Brookhaven National Lab. (BNL), Upton, NY (United States); Meot, F. [Brookhaven National Lab. (BNL), Upton, NY (United States); Mernick, K. [Brookhaven National Lab. (BNL), Upton, NY (United States); Michnoff, R. [Brookhaven National Lab. (BNL), Upton, NY (United States); Minty, M. [Brookhaven National Lab. (BNL), Upton, NY (United States); Montag, C. [Brookhaven National Lab. (BNL), Upton, NY (United States); Morris, J. [Brookhaven National Lab. (BNL), Upton, NY (United States); Narayan, G. [Brookhaven National Lab. (BNL), Upton, NY (United States); Nayak, S. [Brookhaven National Lab. (BNL), Upton, NY (United States); Nemesure, S. [Brookhaven National Lab. (BNL), Upton, NY (United States); Pile, P. [Brookhaven National Lab. (BNL), Upton, NY (United States); Poblaguev, A. [Brookhaven National Lab. (BNL), Upton, NY (United States); Ranjbar, V. [Brookhaven National Lab. (BNL), Upton, NY (United States); Robert-Demolaize, G. [Brookhaven National Lab. (BNL), Upton, NY (United States); Roser, T. [Brookhaven National Lab. (BNL), Upton, NY (United States); Schmidke, B. [Brookhaven National Lab. (BNL), Upton, NY (United States); Schoefer, V. [Brookhaven National Lab. (BNL), Upton, NY (United States); Severino, F. [Brookhaven National Lab. (BNL), Upton, NY (United States); Shrey, T. [Brookhaven National Lab. (BNL), Upton, NY (United States); Smith, K. [Brookhaven National Lab. (BNL), Upton, NY (United States); Steski, D. [Brookhaven National Lab. (BNL), Upton, NY (United States); Tepikian, S. [Brookhaven National Lab. (BNL), Upton, NY (United States); Trbojevic, D. [Brookhaven National Lab. (BNL), Upton, NY (United States); Tsoupas, N. [Brookhaven National Lab. (BNL), Upton, NY (United States); Wang, G. [Brookhaven National Lab. (BNL), Upton, NY (United States); White, S. [Brookhaven National Lab. (BNL), Upton, NY (United States); Yip, K. [Brookhaven National Lab. (BNL), Upton, NY (United States); Zaltsman, A. [Brookhaven National Lab. (BNL), Upton, NY (United States); Zeno, K. [Brookhaven National Lab. (BNL), Upton, NY (United States); Zhang, S. Y. [Brookhaven National Lab. (BNL), Upton, NY (United States)

    2015-08-07

    To study low-x shadowing/saturation physics as well as other nuclear effects [1], [2], proton-gold (p-Au, for 5 weeks) and proton-Aluminum (p-Al, for 2 weeks) collisions were provided for experiments in 2015 at the Relativistic Heavy Ion Collider (RHIC), with polarized proton beam in the Blue ring and Au/Al beam in the Yellow ring. The special features of the asymmetric run in 2015 will be introduced. The operation experience will be reviewed as well in the report.

  7. Neuronal Alignment On Asymmetric Textured Surfaces

    CERN Document Server

    Beighley, Ross; Sekeroglu, Koray; Atherton, Timothy; Demirel, Melik C; Staii, Cristian

    2013-01-01

    Axonal growth and the formation of synaptic connections are key steps in the development of the nervous system. Here we present experimental and theoretical results on axonal growth and interconnectivity in order to elucidate some of the basic rules that neuronal cells use for functional connections with one another. We demonstrate that a unidirectional nanotextured surface can bias axonal growth. We perform a systematic investigation of neuronal processes on asymmetric surfaces and quantify the role that biomechanical surface cues play in neuronal growth. These results represent an important step towards engineering directed axonal growth for neuro-regeneration studies.

  8. Asymmetric Synthesis of Both Enantiomers of Disparlure

    Institute of Scientific and Technical Information of China (English)

    王志刚; 郑剑峰; 黄培强

    2012-01-01

    Starting from propargyl alcohol (12), and on the basis of Zhou's modified Sharpless asymmetric epoxidation, the sex pheromone of the Gypsy moth, disparlure (+)-8 and its enantiomer (-)-8 have been synthesized, each in six steps, with overall yields of 29% for (+)-8 and 27% for (-)-8 (ee〉98%). The use of the sequential coupling tactic renders the method flexible, which is applicable to the synthesis of other cis-epoxy pheromones.

  9. Asymmetric acoustic transmission in graded beam

    Energy Technology Data Exchange (ETDEWEB)

    Jing, Li, E-mail: lj94172350@hotmail.com [School of Mechanical Engineering and State Key laboratory for Strength and Vibration of Mechanical Structures, Xi’an Jiaotong University, Xi’an, Shaanxi 710049 (China); Wu, Jiu Hui, E-mail: ejhwu@mail.xjtu.edu.cn [School of Mechanical Engineering and State Key laboratory for Strength and Vibration of Mechanical Structures, Xi’an Jiaotong University, Xi’an, Shaanxi 710049 (China); Guan, Dong; Lu, Kuan [School of Mechanical Engineering and State Key laboratory for Strength and Vibration of Mechanical Structures, Xi’an Jiaotong University, Xi’an, Shaanxi 710049 (China); Gao, Nansha [School of Marine Science and Technology, Northwestern Polytechnical University, Xi’an, Shaanxi 710072 (China); Songhua, Cao [School of Mechanical Engineering and State Key laboratory for Strength and Vibration of Mechanical Structures, Xi’an Jiaotong University, Xi’an, Shaanxi 710049 (China)

    2016-12-01

    We demonstrate the dynamic effective material parameters and vibration performance of a graded beam. The structure of the beam was composed of several unit cells with different fill factors. The dispersion relations and energy band structures of each unit cell were calculated using the finite element method (FEM). The dynamic effective material parameters in each unit cell of the graded beam were determined by the dispersion relations and energy band structures. Longitudinal wave propagation was investigated using a numerical method and FEM. The results show that the graded beam allows asymmetric acoustic transmission over a wide range of frequencies.

  10. Quantum optics of lossy asymmetric beam splitters

    Science.gov (United States)

    Uppu, Ravitej; Wolterink, Tom A. W.; Tentrup, Tristan B. H.; Pinkse, Pepijn W. H.

    2016-07-01

    We theoretically investigate quantum interference of two single photons at a lossy asymmetric beam splitter, the most general passive 2$\\times$2 optical circuit. The losses in the circuit result in a non-unitary scattering matrix with a non-trivial set of constraints on the elements of the scattering matrix. Our analysis using the noise operator formalism shows that the loss allows tunability of quantum interference to an extent not possible with a lossless beam splitter. Our theoretical studies support the experimental demonstrations of programmable quantum interference in highly multimodal systems such as opaque scattering media and multimode fibers.

  11. Analysis of Asymmetric Piezoelectric Composite Beam

    CERN Document Server

    Chen, J -S; Wu, K -C

    2008-01-01

    This paper deals with the vibration analysis of an asymmetric composite beam composed of glass a piezoelectric material. The Bernoulli's beam theory is adopted for mechanical deformations, and the electric potential field of the piezoelectric material is assumed such that the divergence-free requirement of the electrical displacements is satisfied. The accuracy of the analytic model is assessed by comparing the resonance frequencies obtained by the analytic model with those obtained by the finite element method. The model developed can be used as a tool for designing piezoelectric actuators such as micro-pumps.

  12. On asymmetric causal relationships in Petropolitics

    Directory of Open Access Journals (Sweden)

    Balan Feyza

    2016-01-01

    Full Text Available The aim of this paper is to examine whether the First Law of Petropolitics denominated by Friedman in 2006 is valid for OPEC countries. To do this, this paper analyses the relationship between political risk and oil supply by applying the asymmetric panel causality test suggested by Hatemi-J (2011 to these countries for the period 1984-2014. The results show that the First Law of Petropolitics is valid for Angola, Iraq, Kuwait, Libya, Nigeria, Qatar, Saudi Arabia, and the UAE, given that positive oil supply shocks significantly lead to negative political stability shocks, and negative oil supply shocks significantly lead to positive shocks in political stability.

  13. Asymmetric Laser Radiant Cooling in Storage Rings

    CERN Document Server

    Bulyak, E V; Zimmermann, F

    2011-01-01

    Laser pulses with small spatial and temporal dimensions can interact with a fraction of the electron bunches circulating in Compton storage rings. We studied synchrotron dynamics of such bunches when laser photons scatter off from the electrons with energy higher than the synchronous energy. In this case of ‘asymmetric cooling', as shown theoretically, the stationary energy spread is much smaller than under conditions of regular scattering; the oscillations are damped faster. Coherent oscillations of large amplitude may be damped in one synchrotron period, which makes this method feasible for injection the bunches into a ring in the longitudinal phase space. The theoretical results are validated with simulations.

  14. Resonance phenomena for asymmetric weakly nonlinear oscillator

    Institute of Scientific and Technical Information of China (English)

    钱定边

    2002-01-01

    We establish the coexistence of periodic solution and unbounded solution, the infinity of largeamplitude subharmonics for asymmetric weakly nonlinear oscillator x" + a2x+ - b2x- + h(x) = p(t) with h(±∞) - 0 and xh(x) → +∞(x →∞), assuming that M(τ ) has zeros which are all simple and M(τ ) 0respectively, where M(τ ) is a function related to the piecewise linear equation x" + a2x+ - b2x- = p(t).``

  15. Photoresponse of silicon with asymmetric area contacts

    Science.gov (United States)

    Rabbani, M. Golam; Sundararajan, Jency P.; Verma, Amit; Nekovei, Reza; Khader, Mahmoud M.; Darling, R. B.; Patil, Sunil R.

    2017-01-01

    We report on high performance metal-semiconductor-metal (MSM) photosensors based on asymmetric metal pad areas. The reported devices require a single-step metal deposition, and exhibit large photo response even under zero-bias. Moreover the devices offer fast and stable light switching behavior. Device fabrication and electrical characterization results are presented that are further analyzed with TCAD modeling and simulation. Device simulations show that contact asymmetry along with surface recombination and barrier lowering plays an important role in the MSM I-V characteristics.

  16. Dynamic Conditional Correlations for Asymmetric Processes

    OpenAIRE

    Asai, Manabu; McAleer, Michael

    2011-01-01

    The paper develops two Dynamic Conditional Correlation (DCC) models, namely the Wishart DCC (wDCC) model. The paper applies the wDCC approach to the exponential GARCH (EGARCH) and GJR models to propose asymmetric DCC models. We use the standardized multivariate t-distribution to accommodate heavy-tailed errors. The paper presents an empirical example using the trivariate data of the Nikkei 225, Hang Seng and Straits Times Indices for estimating and forecasting the wDCC-EGARCH and wDCC-GJR mod...

  17. Quantum optics of lossy asymmetric beam splitters

    CERN Document Server

    Uppu, Ravitej; Tentrup, Tristan B H; Pinkse, Pepijn W H

    2016-01-01

    We theoretically investigate quantum interference of two single photons at a lossy asymmetric beam splitter, the most general passive 2$\\times$2 optical circuit. The losses in the circuit result in a non-unitary scattering matrix with a non-trivial set of constraints on the elements of the scattering matrix. Our analysis using the noise operator formalism shows that the loss allows tunability of quantum interference to an extent not possible with a lossless beam splitter. Our theoretical studies support the experimental demonstrations of programmable quantum interference in highly multimodal systems such as opaque scattering media and multimode fibers.

  18. Nanotribology of Symmetric and Asymmetric Liquid Lubricants

    Directory of Open Access Journals (Sweden)

    Shinji Yamada

    2010-03-01

    Full Text Available When liquid molecules are confined in a narrow gap between smooth surfaces, their dynamic properties are completely different from those of the bulk. The molecular motions are highly restricted and the system exhibits solid-like responses when sheared slowly. This solidification behavior is very dependent on the molecular geometry (shape of liquids because the solidification is induced by the packing of molecules into ordered structures in confinement. This paper reviews the measurements of confined structures and friction of symmetric and asymmetric liquid lubricants using the surface forces apparatus. The results show subtle and complex friction mechanisms at the molecular scale.

  19. Asymmetric acoustic transmission in graded beam

    Science.gov (United States)

    Jing, Li; Wu, Jiu Hui; Guan, Dong; Lu, Kuan; Gao, Nansha; Songhua, Cao

    2016-12-01

    We demonstrate the dynamic effective material parameters and vibration performance of a graded beam. The structure of the beam was composed of several unit cells with different fill factors. The dispersion relations and energy band structures of each unit cell were calculated using the finite element method (FEM). The dynamic effective material parameters in each unit cell of the graded beam were determined by the dispersion relations and energy band structures. Longitudinal wave propagation was investigated using a numerical method and FEM. The results show that the graded beam allows asymmetric acoustic transmission over a wide range of frequencies.

  20. Asymmetric joint multifractal analysis in Chinese stock markets

    Science.gov (United States)

    Chen, Yuwen; Zheng, Tingting

    2017-04-01

    In this paper, the asymmetric joint multifractal analysis method based on statistical physics is proposed to explore the asymmetric correlation between daily returns and trading volumes in Chinese stock markets. The result shows asymmetric multifractal correlations exist between return and trading volume in Chinese stock markets. Moreover, when the stock indexes are upward, the fluctuations of returns are always weaker than when they are downward, whether the trading volumes are more or less.

  1. An Asymmetric Block Dynamic Conditional Correlation Multivariate GARCH Model

    OpenAIRE

    Vargas, Gregorio A.

    2006-01-01

    The Block DCC model for determining dynamic correlations within and between groups of financial asset returns is extended to account for asymmetric effects. Simulation results show that the Asymmetric Block DCC model is competitive in in-sample forecasting and performs better than alternative DCC models in out-of-sample forecasting of conditional correlation in the presence of asymmetric effect between blocks of asset returns. Empirical results demonstrate that the model is able to capture ...

  2. Asymmetric Campaigning as a Rational Choice: Planning Considerations

    Science.gov (United States)

    2006-06-01

    Maslow identified five levels: survival, safety, belonging, esteem, and self-actualization. He presented his theory as a pyramid with five layers...to be sustained by actions of the asymmetric opponent. For the media-fed frenzy over constraints and protraction to continue, the asymmetric...lot of people. The reason for this is twofold. First, the actor needs sufficient support to exist and to sustain an asymmetric campaign. Second, the

  3. Theory of (e, 2e) reactions

    Science.gov (United States)

    Byron, F. W.; Joachain, C. J.

    1989-08-01

    A comprehensive survey is given of the theory of (e, 2e) reactions. We begin by discussing the kinematics of these reactions, with special attention devoted to the coplanar asymmetric (Ehrhardt-type) geometry and the fully symmetric geometry in which most of the recent (e, 2e) coincidence measurements have been performed. We then review the foundations of the theory of the ionization of atoms by electron impact, first for one-electron atoms and then for target atoms with N electrons. Next, we discussed the Wannier theory of threshold ionization and its excitations. We then turn to the analysis of (e, 2e) reactions at intermediate and high energies. The theory of fast coplanar asymmetric (e, 2e) reactions is analyzed and it is shown that the eikonal-Born series method successfully accounts for all the dynamical features of these reactions. In particular, it is shown that second order effects are essential in explaining all the features exhibited by the measured by the measured triple differential cross sections at intermediate energies. Finally, we review the theory of fast symmetric (e, 2e) reactions. We consider first the (e, 2e) spectroscopy regime in which the momentum transfer Δ is large, but the recoil momentum Q of the ion is small or moderate. We then turn to the regime of large Δ and large Q, for which second order effects are of paramount importance, so that the coplanar symmetric triple differential cross section exhibits a striking behaviour in the large angle region.

  4. Quantity Discount Scheme in Supply Chain under Asymmetric Information

    Institute of Scientific and Technical Information of China (English)

    LI Ji-bin; PENG Zuo-he

    2007-01-01

    Quantity discount scheme plays an important role in supply chain management. The different quantity discount schemes under symmetric (full) information and asymmetric information, are analyzed by using principal-agent and optimal control theory. As a result, the research reveals that the optimal quantity discount solution under symmetric information is a special case of that under asymmetric information. At the same price, the critical value of quantity discount under asymmetric information is much lower than that under asymmetric information. Therefore, this leads to less cost for retailers and smaller profit for their supplier.

  5. Asymmetric transmission: a generic property of lossy periodic interfaces

    CERN Document Server

    Plum, E; Zheludev, N I

    2010-01-01

    Asymmetric transmission of circularly polarized waves is a well-established property of lossy, anisotropic, two-dimensionally chiral patterns. Here we show that asymmetric transmission can be observed for oblique incidence onto any lossy periodically structured plane. Our results greatly expand the range of natural and artificial materials in which directionally asymmetric transmission can be expected making it a cornerstone electromagnetic effect rather than a curiosity of planar chiral metamaterials. Prime candidates for asymmetric transmission at oblique incidence are rectangular arrays of plasmonic spheres or semiconductor quantum dots, lossy double-periodic gratings and planar metamaterial structures.

  6. Asymmetric cell divisions: a view from plant development.

    Science.gov (United States)

    Abrash, Emily B; Bergmann, Dominique C

    2009-06-01

    All complex multicellular organisms must solve the problem of generating diverse and appropriately patterned cell types. Asymmetric division, in which a single mother cell gives rise to daughters with distinct identities, is instrumental in the generation of cellular diversity and higher-level patterns. In animal systems, there exists considerable evidence for conserved mechanisms of polarization and asymmetric division. Here, we consider asymmetric cell divisions in plants, highlighting the unique aspects of plant cell biology and organismal development that constrain the process, but also emphasizing conceptual and mechanistic similarities with animal asymmetric divisions.

  7. At Low SNR Asymmetric Quantizers Are Better

    CERN Document Server

    Koch, Tobias

    2012-01-01

    We study the capacity of the discrete-time Gaussian channel when its output is quantized with a one-bit quantizer. We focus on the low signal-to-noise ratio (SNR) regime, where communication at very low spectral efficiencies takes place. In this regime a symmetric threshold quantizer is known to reduce channel capacity by 2/pi, i.e., to cause an asymptotic power loss of approximately two decibels. Here it is shown that this power loss can be entirely avoided by using asymmetric threshold quantizers and asymmetric signaling constellations. We prove that in order to avoid this power loss flash-signaling input-distributions are essential. Consequently, one-bit output quantization of the Gaussian channel reduces spectral efficiency. Threshold quantizers are not only asymptotically optimal: as we prove, at every fixed SNR, a threshold quantizer maximizes capacity among all one-bit output quantizers. The picture changes on the Rayleigh-fading channel. In the noncoherent case we show that a one-bit output quantizer ...

  8. Evolutionary stability in the asymmetric volunteer's dilemma.

    Directory of Open Access Journals (Sweden)

    Jun-Zhou He

    Full Text Available It is often assumed that in public goods games, contributors are either strong or weak players and each individual has an equal probability of exhibiting cooperation. It is difficult to explain why the public good is produced by strong individuals in some cooperation systems, and by weak individuals in others. Viewing the asymmetric volunteer's dilemma game as an evolutionary game, we find that whether the strong or the weak players produce the public good depends on the initial condition (i.e., phenotype or initial strategy of individuals. These different evolutionarily stable strategies (ESS associated with different initial conditions, can be interpreted as the production modes of public goods of different cooperation systems. A further analysis revealed that the strong player adopts a pure strategy but mixed strategies for the weak players to produce the public good, and that the probability of volunteering by weak players decreases with increasing group size or decreasing cost-benefit ratio. Our model shows that the defection probability of a "strong" player is greater than the "weak" players in the model of Diekmann (1993. This contradicts Selten's (1980 model that public goods can only be produced by a strong player, is not an evolutionarily stable strategy, and will therefore disappear over evolutionary time. Our public good model with ESS has thus extended previous interpretations that the public good can only be produced by strong players in an asymmetric game.

  9. Instability of asymmetric continuous shaft system

    Science.gov (United States)

    Srinath, R.; Sarkar, Abhijit; Sekhar, A. S.

    2016-11-01

    In this work, the governing equation of asymmetric continuous shaft in inertial frame of reference is studied. In particular, determination of the parameter ranges for the stability or instability of the shaft response is the focus of the present work. The governing equations are a fourth-order coupled partial differential equations containing time dependent coefficients. The equations are non-dimensionalized in terms of two parameters related to the average moment of inertia and the difference of moments of inertia about the principal axes. Using the latter as the asymptotic parameter and employing modal superposition, a formal methodology based on perturbation methods is developed to ascertain the stability and instability characteristics. The methodology is applicable to shafts subjected to some of the classical boundary conditions viz. simply supported, cantilever, and fixed-fixed. Similar stability curves are obtained for each mode for these different boundary conditions. The novel non-dimensionalization scheme chosen leads to the stability boundaries as well as the loci of varying speeds to be in the form of straight lines. The intersection of these lines determine the stable and unstable speed ranges of different asymmetric shafts. The results are generalized for different material and geometric properties of the shaft.

  10. Asymmetric disassembly and robustness in declining networks.

    Science.gov (United States)

    Saavedra, Serguei; Reed-Tsochas, Felix; Uzzi, Brian

    2008-10-28

    Mechanisms that enable declining networks to avert structural collapse and performance degradation are not well understood. This knowledge gap reflects a shortage of data on declining networks and an emphasis on models of network growth. Analyzing >700,000 transactions between firms in the New York garment industry over 19 years, we tracked this network's decline and measured how its topology and global performance evolved. We find that favoring asymmetric (disassortative) links is key to preserving the topology and functionality of the declining network. Based on our findings, we tested a model of network decline that combines an asymmetric disassembly process for contraction with a preferential attachment process for regrowth. Our simulation results indicate that the model can explain robustness under decline even if the total population of nodes contracts by more than an order of magnitude, in line with our observations for the empirical network. These findings suggest that disassembly mechanisms are not simply assembly mechanisms in reverse and that our model is relevant to understanding the process of decline and collapse in a broad range of biological, technological, and financial networks.

  11. Coil-Type Asymmetric Supercapacitor Electrical Cables.

    Science.gov (United States)

    Yu, Zenan; Moore, Julian; Calderon, Jean; Zhai, Lei; Thomas, Jayan

    2015-10-21

    Cable-shaped supercapacitors (SCs) have recently aroused significant attention due to their attractive properties such as small size, lightweight, and bendability. Current cable-shaped SCs have symmetric device configuration. However, if an asymmetric design is used in cable-shaped supercapacitors, they would become more attractive due to broader cell operation voltages, which results in higher energy densities. Here, a novel coil-type asymmetric supercapacitor electrical cable (CASEC) is reported with enhanced cell operation voltage and extraordinary mechanical-electrochemical stability. The CASECs show excellent charge-discharge profiles, extraordinary rate capability (95.4%), high energy density (0.85 mWh cm(-3)), remarkable flexibility and bendability, and superior bending cycle stability (≈93.0% after 4000 cycles at different bending states). In addition, the CASECs not only exhibit the capability to store energy but also to transmit electricity simultaneously and independently. The integrated electrical conduction and storage capability of CASECS offer many potential applications in solar energy storage and electronic gadgets. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Asymmetric negotiation in structured language games

    Science.gov (United States)

    Yang, Han-Xin; Wang, Wen-Xu; Wang, Bing-Hong

    2008-02-01

    We propose an asymmetric negotiation strategy to investigate the influence of high-degree agents on the agreement dynamics in a structured language game, the naming game. We introduce a model parameter, which governs the frequency of high-degree agents acting as speakers in communication. It is found that there exists an optimal value of the parameter that induces the fastest convergence to a global consensus on naming an object for both scale-free and small-world naming games. This phenomenon indicates that, although a strong influence of high-degree agents favors consensus achievement, very strong influences inhibit the convergence process, making it even slower than in the absence of influence of high-degree agents. Investigation of the total memory used by agents implies that there is some trade-off between the convergence speed and the required total memory. Other quantities, including the evolution of the number of different names and the relationship between agents’ memories and their degrees, are also studied. The results are helpful for better understanding of the dynamics of the naming game with asymmetric negotiation strategy.

  13. Algebraic Davis Decomposition and Asymmetric Doob Inequalities

    Science.gov (United States)

    Hong, Guixiang; Junge, Marius; Parcet, Javier

    2016-09-01

    In this paper we investigate asymmetric forms of Doob maximal inequality. The asymmetry is imposed by noncommutativity. Let {({M}, τ)} be a noncommutative probability space equipped with a filtration of von Neumann subalgebras {({M}_n)_{n ≥ 1}}, whose union {bigcup_{n≥1}{M}_n} is weak-* dense in {{M}}. Let {{E}_n} denote the corresponding family of conditional expectations. As an illustration for an asymmetric result, we prove that for {1 spaces {{H}_p^r({M})} and {{H}_p^c({M})} respectively. In particular, this solves a problem posed by the Defant and Junge in 2004. In the case p = 1, our results establish a noncommutative form of the Davis celebrated theorem on the relation betwe en martingale maximal and square functions in L 1, whose noncommutative form has remained open for quite some time. Given {1 ≤ p ≤ 2}, we also provide new weak type maximal estimates, which imply in turn left/right almost uniform convergence of {{E}_n(x)} in row/column Hardy spaces. This improves the bilateral convergence known so far. Our approach is based on new forms of Davis martingale decomposition which are of independent interest, and an algebraic atomic description for the involved Hardy spaces. The latter results are new even for commutative von Neumann algebras.

  14. An asymmetric B factory based on PEP

    Energy Technology Data Exchange (ETDEWEB)

    1991-02-01

    In this report we describe a design for a high-luminosity Asymmetric B Factory to be built in the PEP tunnel on the SLAC site. This proposal, a collaborative effort SLAC, LBL, and LLNL, is the culmination of more than two years of effort aimed at the design and construction of an asymmetric e{sup +}e{sup {minus}} collider capable of achieving a luminosity of L = 3 {times} 10{sup 33} cm{sup {minus}2} s{sup {minus}1}. The configuration adopted utilizes two storage rings, and electron ring operating at 9 GeV and a positron ring at 3.1 GeV, each with a circumference of 2200 m. The high-energy ring is an upgrade of the PEP storage ring at SLAC; all PEP magnets and most power supplies will be reused. The upgrade consists primarily of replacing the PEP vacuum chamber and RF system with newly designed versions optimized for the high-current environment of the B Factory. The low-energy ring will be newly constructed and will be situated atop the high-energy ring in the PEP tunnel. Utilities already installed in the PEP tunnel are largely sufficient to operate the two B Factory storage rings.

  15. Asymmetric DSL Technology of Signal Transmission

    Directory of Open Access Journals (Sweden)

    Dražen Kovačević

    2005-05-01

    Full Text Available Asymmetric flow of information is the key feature of theADSL (Asymmetric Digital Subscriber Loop technology, i.e.higher data transmission rate towards the user than from theuser towards the network. Characteristic is the short messagesending by the user with a certain request to the se!Ver. These!Ver responds to the request by a significantly longer messageof various electronic forms (data, digitized speech, pictures orvideo. Therefore, this technology is most often used by smalland medium users. ADSL is currently the only commerciallyavailable DSL technology which is still experiencing the breakthroughon the seiVice market. It enables faster access to theInternet, LAN (Local Area Network, videoconferencing, VoD(Video on Demand and interactive multimedia. In order tostandardize such se/Vices, the !TU (International TelecommunicationsUnion G. 992.1 (standardized DMT-discrete multi-tone line coding technology and ANSJ (American NationalStandards Institution Tl.413-95!98 are used for ADSL. DMT(Discrete Multi Tone, as the more popular one, uses the linecoding technique, which splits a certain frequency range intoseveral sub-channels. Most of these sub-channels are used forupstream and downstream transmission of speech and data,whereas some are used as pilot signals or kept in rese/Ve. Suchmodulation technique expands the frequency spectrum, allowingthe usage ofbroadband se/Vices per one pair of wires. In thisway the sharing of speech and data se/Vice transmission is realized.

  16. Properties of asymmetrically evolved community networks

    Institute of Scientific and Technical Information of China (English)

    Cui Di; Gao Zi-You; Zheng Jian-Feng

    2009-01-01

    This paper studies a simple asymmetrically evolved community network with a combination of preferential at-tachment and random properties. An important issue about community networks is to discover the different utility increments of two nodes, where the utility is introduced to investigate the asymmetrical effect of connecting two nodes. On the other hand, the connection of two nodes in community networks can be classified as two nodes belonging to the same or to different communities. The simulation results show that the model can reproduce a power-law utility distribution P(u)~ u-σ,σ=2+ 1/p, which can be obtained by using mean-field approximation methods. Furthermore, the model exhibits exponential behaviour with respect to small values of a parameter denoting the random effect in our model at the low-utility region and a power-law feature with respect to big values of this parameter at the high-utility region, which is in good agreement with theoretical analysis. This kind of community network can reproduce a unique utility distribution by theoretical and numerical analysis.

  17. [Asymmetric hypertrophy of the masticatory muscles].

    Science.gov (United States)

    Arzul, L; Corre, P; Khonsari, R H; Mercier, J-M; Piot, B

    2012-06-01

    Hypertrophy of the masticatory muscles most commonly affects the masseter. Less common cases of isolated or associated temporalis hypertrophy are also reported. Parafunctional habits, and more precisely bruxism, can favor the onset of the hypertrophy. This condition is generally idiopathic and can require both medical and/or surgical management. A 29-year-old patient was referred to our department for an asymmetric swelling of the masticatory muscles. Physical examination revealed a bilateral hypertrophy of the masticatory muscles, predominantly affecting the right temporalis and the left masseter. Major bruxism was assessed by premature dental wearing. The additional examinations confirmed the isolated muscle hypertrophy. Benign asymmetric hypertrophy of the masticatory muscles promoted by bruxism was diagnosed. Treatment with injections of type A botulinum toxin was conducted in association with a splint and relaxation. Its effectiveness has been observed at six months. Few cases of unilateral or bilateral temporalis hypertrophy have been reported, added to the more common isolated masseter muscles hypertrophy. The diagnosis requires to rule out secondary hypertrophies and tumors using Magnetic Resonance Imaging. The condition is thought to be favoured by parafunctional habits such as bruxism. The conservative treatment consists in reducing the volume of the masticatory muscles using intramuscular injections of type A botulinum toxin. Other potential conservative treatments are wearing splints and muscle relaxant drugs. Surgical procedures aiming to reduce the muscle volume and/or the bone volume (mandibular gonioplasty) can be proposed. Copyright © 2012 Elsevier Masson SAS. All rights reserved.

  18. Asymmetric transition disks: Vorticity or eccentricity?

    CERN Document Server

    Zsom, A; Ghanbari, J

    2013-01-01

    Context. Transition disks typically appear in resolved millimeter observations as giant dust rings surrounding their young host stars. More accurate observations with ALMA have shown several of these rings to be in fact asymmetric: they have lopsided shapes. It has been speculated that these rings act as dust traps, which would make them important laboratories for studying planet formation. It has been shown that an elongated giant vortex produced in a disk with a strong viscosity jump strikingly resembles the observed asymmetric rings. Aims. We aim to study a similar behavior for a disk in which a giant planet is embedded. However, a giant planet can induce two kinds of asymmetries: (1) a giant vortex, and (2) an eccentric disk. We studied under which conditions each of these can appear, and how one can observationally distinguish between them. This is important because only a vortex can trap particles both radially and azimuthally, while the eccentric ring can only trap particles in radial direction. Method...

  19. Survey of Reflection-Asymmetric Nuclear Deformations

    Science.gov (United States)

    Olsen, Erik; Cao, Yuchen; Nazarewicz, Witold; Schunck, Nicolas

    2016-09-01

    Due to spontaneous symmetry breaking it is possible for a nucleus to have a deformed shape in its ground state. It is theorized that atoms whose nuclei have reflection-asymmetric or pear-like deformations could have non-zero electric dipole moments (EDMs). Such a trait would be evidence of CP-violation, a feature that goes beyond the Standard Model of Physics. It is the purpose of this project to predict which nuclei exhibit a reflection-asymmetric deformation and which of those would be the best candidates for an EDM measuring experiment. Using nuclear Density Functional Theory along with the new computer code AxialHFB and massively parallel computing we calculated ground state nuclear properties for thousands of even-even nuclei across the nuclear chart: from light to superheavy and from stable to short-lived systems. Six different Energy Density Functionals (EDFs) were used to assess systematic errors in our calculations. These results are to be added to the website Massexplorer (http://massexplorer.frib.msu.edu/) which contains results from earlier mass table calculations and information on single quasiparticle energies.

  20. Substituent effect in the photochromism of two isomeric asymmetric diarylethenes having pyrrole and thiophene units

    Science.gov (United States)

    Wang, Renjie; Zhang, Xiaoxia; Pu, Shouzhi; Liu, Gang; Dai, Yanfeng

    2017-02-01

    Two new asymmetric isomeric diarylethenes having pyrrole and thiophene units have been synthesized by one-pot reaction and characterized by single crystal X-ray diffraction analysis. The two prepared diarylethenes had disparate crystal structures, and they exhibited distinctly different photochromic behavior, both in solution and in the solid state. Their photochromism, fatigue resistance, and fluorescence were investigated systematically. The methyl group at the reactive carbon atom could significantly enhance the quantum yield of cyclization step and decrease the quantum yield of cycloreversion step, whereas a cyano group at the same position could notably suppress the photocyclization reaction and promote the photocycloreversion reaction. The results indicated that the substituent at the reactive carbon atom could readily modulate the optoelectronic and physical properties for these diarylethenes.

  1. Iridium-catalyzed asymmetric ring-opening of oxabenzonorbornadienes with phenols.

    Science.gov (United States)

    Cheng, Hanchao; Yang, Dingqiao

    2012-11-02

    A novel iridium-catalyzed asymmetric ring-opening (ARO) reaction of oxabenzonorbornadienes with a variety of phenols was reported, which afforded the corresponding trans-2-phenoxy-1,2-dihydronaphthalen-1-ol products in high yields with moderate to excellent enantioselectivities (up to 98% ee) under mild conditions. The trans products are formed via the enantioselective cleavage of a bridgehead carbon-oxygen bond in 1 followed by S(N)2 nucleophilic attack by phenols. The effects of various bisphosphine ligands, Ag (I) salts, ammonium halides, bases, and solvents on the yield and enantioselectivity of the reaction were also investigated. The trans-configuration of the product 2a was confirmed by X-ray crystal structure analysis. A possible mechanism for the present catalytic reaction was proposed.

  2. Symmetric and asymmetric ternary fission of hot nuclei

    Science.gov (United States)

    Siwek-Wilczynska, K.; Wilczynski, J.; Leegte, H. K. W.; Siemssen, R. H.; Wilschut, H. W.; Grotowski, K.; Panasiewicz, A.; Sosin, Z.; Wieloch, A.

    1993-07-01

    Emission of α particles accompanying fusion-fission processes in the 40Ar +232Th reaction at E(40Ar) = 365 MeV was studied in a wide range of in-fission-plane and out-of-plane angles. The exact determination of the emission angles of both fission fragments combined with the time-of-flight measurements allowed us to reconstruct the complete kinematics of each ternary event. The coincident energy spectra of α particles were analyzed by using predictions of the energy spectra of the statistical code cascade . The analysis clearly demonstrates emission from the composite system prior to fission, emission from fully accelerated fragments after fission, and also emission during scission. The analysis is presented for both symmetric and asymmetric fission. The results have been analyzed using a time-dependent statistical decay code and confronted with dynamical calculations based on a classical one-body dissipation model. The observed near-scission emission is consistent with evaporation from a dinuclear system just before scission and evaporation from separated fragments just after scission. The analysis suggests that the time scale of fission of the hot composite systems is long (about 7×10-20 s) and the motion during the descent to scission almost completely damped.

  3. Kinetic Study of [2]Pseudorotaxane Formation with an Asymmetrical Thread.

    Science.gov (United States)

    Quiroga, Miguel; Parajó, Mercedes; Rodríguez-Dafonte, Pedro; García-Río, Luis

    2016-06-28

    Kinetic and thermodynamic studies on cyclodextrin (CD)-based [2]pseudorotaxane formation have been carried out by a combination of NMR and calorimetric techniques using bolaform surfactants as axles. Experimental evidence of the formation of an external complex between the trimethylammonium head groups of the axle and the external hydrogen atoms of α-cyclodextrin (α-CD) is reported. Inclusion of this external complex in the reaction pathway allows us to explain the kinetic behavior as well as the nonlinear dependence of the observed rate constant on CD concentrations. The equilibrium constant for [2]pseudorotaxane formation is strongly affected by the spacer length of the axle. This effect is a consequence of increasing rotaxane stability because the threading rate constant is almost independent of the spacer length, but dethreading strongly decreases on increasing the axle size. Using a nonsymmetrical axle with tripropyl and trimethylammonium cations precludes CD threading by the large head side. CDs will thread this asymmetrical bolaform by both their wide and narrow sides, yielding two isomeric [2]pseudorotaxanes. Threading by the wide side of the CD is 60% more favorable than that by the narrow one, but dethreading rate constants are the same for both isomers.

  4. Asymmetric Transfer Hydrogenation of ω -Bromo Acetophenones in Aqueous Media

    Institute of Scientific and Technical Information of China (English)

    Wang Fei; Liu Hui; Cui Xin; Cun Linfeng; Zhu Jin; Deng Jingen; Jiang Yaozhong

    2004-01-01

    Optical active ω-bromophenylethanols are useful building blocks for synthesis of various pharmaceuticals such as α 1-, β 2-, and β 3- adrenergic receptor agonists, which are always obtained though a biotransformative pathway and using boron reagent with rigorous conditions [1]. To our knowledge, the metal-catalysed transfer hydrogenation is seldom applied in this reaction. Recently we have developed a water-soluble chiral Ru-complex and applied successfully in transfer hydrogenation of ω-bromo acetophenones in aqueous media [2], which can not be performed in homogeneous system with HCOOH/NEt3 as hydrogen donor[3] .In this paper, we will report that asymmetric transfer hydrogenation of ω-bromo acetophenones was successfully performed in aqueous media by employing hydrophobic Rh-amido complex (TsDPEN-Rh) as catalyst and HCOONa as hydrogen donor. Moreover, marked increasing of activity and high enantioselectivity (up to 98%) of ω-bromo acetophenone 1a was found in the presence of different micelles or vesicles. This method was also applied successfully in preparation of the important chiral medicinal intermediates, such as the precursor of salbutamol, 2b and fermoterol, 2c with high enantioselectivity.

  5. Asymmetric Suzuki-Miyaura coupling of heterocycles via Rhodium-catalysed allylic arylation of racemates

    Science.gov (United States)

    Schäfer, Philipp; Palacin, Thomas; Sidera, Mireia; Fletcher, Stephen P.

    2017-06-01

    Using asymmetric catalysis to simultaneously form carbon-carbon bonds and generate single isomer products is strategically important. Suzuki-Miyaura cross-coupling is widely used in the academic and industrial sectors to synthesize drugs, agrochemicals and biologically active and advanced materials. However, widely applicable enantioselective Suzuki-Miyaura variations to provide 3D molecules remain elusive. Here we report a rhodium-catalysed asymmetric Suzuki-Miyaura reaction with important partners including aryls, vinyls, heteroaromatics and heterocycles. The method can be used to couple two heterocyclic species so the highly enantioenriched products have a wide array of cores. We show that pyridine boronic acids are unsuitable, but they can be halogen-modified at the 2-position to undergo reaction, and this halogen can then be removed or used to facilitate further reactions. The method is used to synthesize isoanabasine, preclamol, and niraparib--an anticancer agent in several clinical trials. We anticipate this method will be a useful tool in drug synthesis and discovery.

  6. Microbial transformations 59: first kilogram scale asymmetric microbial Baeyer-Villiger oxidation with optimized productivity using a resin-based in situ SFPR strategy.

    Science.gov (United States)

    Hilker, Iris; Wohlgemuth, Roland; Alphand, Véronique; Furstoss, Roland

    2005-12-20

    This study is demonstrating the scale up of asymmetric microbial Baeyer-Villiger oxidation of racemic bicyclo[3.2.0]hept-2-en-6-one (1) to the kilogram scale using a 50 L bioreactor. The process has been optimized with respect to bottlenecks identified in downscaled experiments. A high productivity was obtained combining a resin-based in situ substrate feeding and product removal methodology (in situ SFPR), a glycerol feed control, and an improved oxygenation device (using a sintered-metal sparger). As expected both regioisomeric lactones [(-)-(1S,5R)-2 and (-)-(1R,5S)-3] were obtained in nearly enantiopure form (ee > 98%) and good yield. This represents the first example of such an asymmetric Baeyer-Villiger biooxidation reaction ever operated at that scale. This novel resin-based in situ SFPR technology therefore clearly opens the way to further (industrial) upscaling of this highly valuable (asymmetric) reaction.

  7. Synthesis of Asymmetrical Organic Carbonates using CO2 as a Feedstock in AgCl/Ionic Liquid System at Ambient Conditions.

    Science.gov (United States)

    Hu, Jiayin; Ma, Jun; Lu, Lu; Qian, Qingli; Zhang, Zhaofu; Xie, Chao; Han, Buxing

    2017-03-22

    Synthesis of asymmetrical organic carbonates from the renewable and inexpensive CO2 is of great importance but also challenging, especially at ambient conditions. Herein, we found that some metal salt/ionic liquid catalyst systems were highly active for the synthesis of asymmetrical organic carbonates from CO2 , propargylic alcohols, and primary alcohols. Especially, the AgCl/1-butyl-3-methylimidazolium acetate ([Bmim][OAc]) system was very efficient for the reactions of a wide range of substrates at room temperature and atmospheric pressure, and the yields of the asymmetrical organic carbonates could approach 100 %. The catalyst system could be reused at least five times without changing its catalytic performance, and could be easily recovered and reused. A detailed study indicated that AgCl and [Bmim][OAc] catalyzed the reactions cooperatively, resulting in unique catalytic performance. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Ruthenium complexes with chiral tetradentate PNNP ligands: asymmetric catalysis from the viewpoint of inorganic chemistry.

    Science.gov (United States)

    Mezzetti, Antonio

    2010-09-14

    This is a personal account of the application of ruthenium complexes containing chiral tetradentate ligands with a P(2)N(2) ligand set (PNNP) as catalyst precursors for enantioselective "atom transfer" reactions. Therewith are meant reactions that involve bond formation between a metal-coordinated molecule and a free reagent. The reactive fragment (e.g. carbene) is transferred either from the metal to the non-coordinated substrate (e.g. olefin) or from the free reagent (e.g. F(+)) to the metal-bound substrate (e.g.beta-ketoester), depending on the class of catalyst (monocationic, Class A; or dicationic, Class B). The monocationic five-coordinate species [RuCl(PNNP)](+) and the six-coordinate complexes [RuCl(L)(PNNP)](+) (L = Et(2)O, H(2)O) of Class A catalyse asymmetric epoxidation, cyclopropanation (carbene transfer from the metal to the free olefin), and imine aziridination. Alternatively, the dicationic complexes [Ru(L-L)(PNNP)](2+) (Class B), which contain substrates that act as neutral bidentate ligands L-L (e.g., beta-ketoesters), catalyse Michael addition, electrophilic fluorination, and hydroxylation reactions. Additionally, unsaturated beta-ketoesters form dicationic complexes of Class B that catalyse Diels-Alder reactions with acyclic dienes to produce tetrahydro-1-indanones and estrone derivatives. Excellent enantioselectivity has been achieved in several of the catalytic reactions mentioned above. The study of key reaction intermediates (both in the solid state and in solution) has revealed significant mechanistic aspects of the catalytic reactions.

  9. Photonic integration using asymmetric twin-waveguides

    Science.gov (United States)

    Studenkov, Pavel V.

    A novel approach to fabrication of monolithic photonic integrated circuits based on the asymmetric twin- waveguide (ATG) structure is proposed and demonstrated. In contrast to the conventional integration methods relying on semiconductor regrowth, the ATG approach requires only one epitaxy step, while the integrated devices are defined by post-growth patterning. The ATG structure contains two evanescently coupled waveguide layers separated by a cladding layer. The upper layer provides optical gain for the active devices such as lasers and semiconductor optical amplifiers. The transparent lower layer is used to make waveguides and optical interconnects on the chip. Thus the ATG represents a versatile integration platform for cost- effective fabrication of photonic integrated circuits, similar in some respects to the electronic CMOS platform. Light propagation and coupling in the ATG structure are analyzed using the beam propagation method to optimize the layer design. It is shown that the asymmetric refractive index profile eliminates undesirable optical coupling between the waveguide layers. At the interfaces between the active and passive devices, lateral tapers are used to induce vertical coupling of light with a coupling loss of typically integrated devices can be separately optimized to achieve performance close to that of the conventional discrete components. The design of taper couplers is described in detail, and their performance is experimentally verified. Using the ATG approach, several integrated devices were fabricated in the InGaAsP/InP material system for λ = 1.55 μm wavelength operation. Lasers and semiconductor optical amplifiers with integrated waveguides were characterized to test the integration approach. Single-frequency, distributed Bragg reflector (DBR) lasers achieved output power of 11 mW with a 40 dB side-mode suppression ratio. A DBR laser with integrated electroabsorption modulator had a 24 dB extinction ratio between 0V and -2V bias

  10. Asymmetric group loans, non-assortative matching and adverse selection

    NARCIS (Netherlands)

    Gangopadhyay, Shubhashis; Lensink, Robert

    2014-01-01

    This paper shows that an asymmetric group debt contract, where one borrower co-signs for another, but not vice versa, leads to heterogeneous matching. The analysis suggests that micro finance organizations can achieve the first best by offering asymmetric group contracts. (C) 2014 Elsevier B.V. All

  11. A rationale for the preparation of asymmetric pervaporation membranes

    NARCIS (Netherlands)

    Mulder, M.H.V.; Oude Hendrikman, J.; Wijmans, J.G.; Smolders, C.A.

    1985-01-01

    Pervaporation is carried out primarily with homogeneous membranes. An improvement in permeation rate can be achieved by using asymmetric or composite membranes. In order to maintain a high selectivity, very dense top layers are needed. The formation of asymmetric pervaporation membranes will be disc

  12. Extensive Taguchi's Quality Loss Function Based On Asymmetric tolerances

    Institute of Scientific and Technical Information of China (English)

    ZHU Wei; LI Yuan-sheng; LIU Feng

    2004-01-01

    If specification interval is asymmetric, basic specification is the target value of quality characteristics. In this paper Taguchi's quality loss function is applied to describe quality loss based on asymmetric tolerances. The measurement of quality loss which is caused by the deviation of quality characteristics from basic specification is further presented.

  13. Current Large Deviations for Asymmetric Exclusion Processes with Open Boundaries

    Science.gov (United States)

    Bodineau, T.; Derrida, B.

    2006-04-01

    We study the large deviation functional of the current for the Weakly Asymmetric Simple Exclusion Process in contact with two reservoirs. We compare this functional in the large drift limit to the one of the Totally Asymmetric Simple Exclusion Process, in particular to the Jensen-Varadhan functional. Conjectures for generalizing the Jensen-Varadhan functional to open systems are also stated.

  14. ASYMMETRIC HYDROSILYLATION CATALYZED BY POLYMER—SUPPORTED THIAZOLIDINE RHODIUM CATALYSTS

    Institute of Scientific and Technical Information of China (English)

    LEIYanohui; LIHong; 等

    1999-01-01

    Asymmetric hydrisilylation catalyzed by polymeric thiazolidine rhodium catalysts was conducted.Almost the same optical yields have been obtained when comb-shaped polymeric ligands and their corresponding monomer complexed rhodium cataltysts were used to asymmetric hydrosilylation of acetophenone.Optical yield of chiral 1-methylbenzyl alcohol reaches as high as 71.5%.Temperature dependence of enantioselective hydrosilylation of acetophenone was discussed.

  15. A new convenient asymmetric approach to herbarumin Ⅲ

    Institute of Scientific and Technical Information of China (English)

    Xue Song Chen; Shi Jun Da; Li Hong Yang; Bo Yan Xu; Zhi Xiang Xie; Ying Li

    2007-01-01

    The asymmetric total synthesis of herbarumin Ⅲ 3, a naturally occurred phytotoxin, along with 8-epi-herbarumin Ⅲ 22, was succeeded in 12 steps from n-butyraldehyde based on Brown's asymmetric allylation, taking modified Julia olefination and Yamaguchi's macro-lactonization as key steps.

  16. Effect of asymmetric auxin application on Helianthus hypocotyl curvature

    Science.gov (United States)

    Migliaccio, F.; Rayle, D. L.

    1989-01-01

    Indole-3-acetic acid was applied asymmetrically to the hypocotyls of sunflower (Helianthus annuus L.) seedlings. After 5 hours on a clinostat, auxin gradients as small as 1 to 1.3 produced substantial (more than 60 degrees) hypocotyl curvature. This result suggests the asymmetric growth underlying hypocotyl gravitropism can be explained by lateral auxin redistribution.

  17. Development of a Novel, Oxidatively Activated, Safety-Catch Linker for Solid-Phase Asymmetric Organic Synthesis (SPOS)

    Institute of Scientific and Technical Information of China (English)

    LIN,Jun; Hjalmar Skarphedinsson; Stepehen G.Davies

    2004-01-01

    @@ Solid-phase asymmetric organic synthesis has become a very important synthetic strategy within the organic chemistry community.[1] Critical to success in SPOS is a linking strategy which allows both the substrate to be loaded and the product released efficiently from the polymeric support. A safety catch linker[2] (SCL) is in principle a linking molecule orthogonal to the reaction conditions of the library synthesis, which can be easily activated by a simple chemical transformation to allow efficient cleavage of the products from the polymer under mild conditions. In order to introduce the SuperQuat chiral auxiliaries[3] for SOPS, we report herein design and synthesis of a novel safety catch linker for asymmetric conjugate addition reactions.

  18. Asymmetric synthesis of tertiary alcohols by the use of tricarbonylchromium (O) complexes

    Energy Technology Data Exchange (ETDEWEB)

    Furtado, O.R.; Gomes Costa, M.R.; Marcelo Curto, M.J. [Instituto Nacional de Engenharia e Tecnolgia Industrial, Queluz (Portugal)] [and others

    1995-12-31

    The demand for homochiral compounds by the pharmaceutical and related industries has stimulated great interest in the development of asymmetric methodology for organic synthesis. The authors report herein the stereoselective synthesis of tertiary benzylic alcohols. These homochiral tertiary alcohols could be obtained by stereoselective addition to the carbonyl function of chiral [(aryl)Cr(CO){sub 3}] ketones. The syntheses of these ketones were performed by reaction of lithiated (arene)Cr(CO){sub 3} complexes with acyl halides or aldehydes followed by Swern oxidation of the alcohols obtained.

  19. A New Complex with Good Catalytic Properties in Asymmetric Synthesis of Cyclopropanecarboxylic Acids

    Institute of Scientific and Technical Information of China (English)

    CAI Ya; ZHENG He-Gen; XIN Xin-Quan

    2003-01-01

    @@ The chemistry of transition metal-sulfur clusters has attracted much attention recently owing to their relevance to certain biological and industrial catalyses, rich structural chemistry, and special reactive properties as well as potential application in nonlinear optical materials. [1~ 3] In this article, a new complex, WCu2S4 (dppf)2 [ dppf = 1, 1′bis(diphenylphosphino)ferrocene] was synthesized through solid state reaction, and it was found that this complex had good catalytic properties in asymmetric synthesis of cyclopropanecarboxylic acids.

  20. An Asymmetric Organocatalytic Quadruple Cascade to Tetraaryl-Substituted 2-Azabicyclo[3.3.0]octadienones

    Science.gov (United States)

    Joie, Céline; Deckers, Kristina; Raabe, Gerhard; Enders, Dieter

    2014-01-01

    A new asymmetric organocatalytic three-component quadruple cascade of α-ketoamides with α,β-unsaturated aldehydes is described. The reaction is catalyzed by the (S)-diphenylprolinol TMS ether catalyst and proceeds via an aza-Michael/aldol condensation/vinylogous Michael/aldol condensation sequence to yield tetraaryl-substituted 2-azabicyclo[3.3.0]octadienone derivatives. The cascade products are obtained with good to very good yields (34–71%), virtually complete diastereoselectivities (>20:1), and very good enantioselectivities (84–97%). PMID:25278633