WorldWideScience

Sample records for palladium-catalyzed 5-exo-dig annulation

  1. Synthesis of Dihydrobenzofurans via Palladium-Catalyzed Heteroannulations

    Energy Technology Data Exchange (ETDEWEB)

    Rozhkov, Roman Vladimirovich [Iowa State Univ., Ames, IA (United States)

    2004-01-01

    Palladium-catalyzed heteroannulation of 1,3-dienes with 3-iodo-2-alkenols, and 2-iodo-2-alkenols, as well as their amino analogs, affords the corresponding cyclic ethers and amines respectively. The presence of a β-hydrogen in the vinylic halide results in β-hydride elimination giving the corresponding alkyne. The presence of a bulky group in the α-position of the vinylic halide results in failure or reduced amounts of annulation products. A chloride source, pyridine base and electron-rich phosphine are essential for this reaction.

  2. New Palladium-Catalyzed Approaches to Heterocycles and Carbocycles

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Qinhua [Iowa State Univ., Ames, IA (United States)

    2004-12-19

    The tert-butylimines of o-(1-alkynyl)benzaldehydes and analogous pyridinecarbaldehydes have been cyclized under very mild reaction conditions in the presence of I2, ICl, PhSeCl, PhSCl and p-O2NC6H4SCl to give the corresponding halogen-, selenium- and sulfur-containing disubstituted isoquinolines and naphthyridines, respectively. Monosubstituted isoquinolines and naphthyridines have been synthesized by the metal-catalyzed ring closure of these same iminoalkynes. This methodology accommodates a variety of iminoalkynes and affords the anticipated heterocycles in moderate to excellent yields. The Pd(II)-catalyzed cyclization of 2-(1-alkynyl)arylaldimines in the presence of various alkenes provides an efficient way to synthesize a variety of 4-(1-alkenyl)-3-arylisoquinolines in moderate to excellent yields. The introduction of an ortho-methoxy group on the arylaldimine promotes the Pd-catalyzed cyclization and stabilizes the resulting Pd(II) intermediate, improving the yields of the isoquinoline products. Highly substituted naphthalenes have been synthesized by the palladium-catalyzed annulation of a variety of internal alkynes, in which two new carbon-carbon bonds are formed in a single step under relatively mild reaction conditions. This method has also been used to synthesize carbazoles, although a higher reaction temperature is necessary. The process involves arylpalladation of the alkyne, followed by intramolecular Heck olefination and double bond isomerization. This method accommodates a variety of functional groups and affords the anticipated highly substituted naphthalenes and carbazoles in good to excellent yields. Novel palladium migratiodarylation methodology for the synthesis of complex fused polycycles has been developed, in which one or more sequential Pd-catalyzed intramolecular migration processes involving C-H activation are employed. The chemistry works best with electron-rich aromatics, which is in agreement

  3. Transition-metal-free synthesis of imidazo[2,1-b]thiazoles and thiazolo[3,2-a]benzimidazoles via an S-propargylation/5-exo-dig cyclization/isomerization sequence using propargyl tosylates as substrates.

    Science.gov (United States)

    Omar, Mohamed A; Frey, Wolfgang; Conrad, Jürgen; Beifuss, Uwe

    2014-11-07

    A transition-metal-free route for the synthesis of several N-fused heterocycles, including thiazolo[3,2-a]benzimidazoles and imidazo[2,1-b]thiazoles, is reported. The reaction between propargyl tosylates and 2-mercaptobenzimidazoles under basic conditions results in 3-substituted thiazolo[3,2-a]benzimidazoles, in yields up to 92% in a single synthesis step. With 2-mercaptoimidazoles as the substrate, the corresponding imidazo[2,1-b]thiazoles were exclusively obtained. The transformation is considered to proceed as an intermolecular S-propargylation that is followed by 5-exo-dig ring closure and double-bond isomerization.

  4. Palladium-catalyzed allylation of tautomerizable heterocycles with alkynes.

    Science.gov (United States)

    Lu, Chuan-Jun; Chen, Dong-Kai; Chen, Hong; Wang, Hong; Jin, Hongwei; Huang, Xifu; Gao, Jianrong

    2017-07-21

    A method for the allylic amidation of tautomerizable heterocycles was developed by a palladium catalyzed allylation reaction with 100% atom economy. A series of structurally diverse N-allylic substituted heterocycles can be synthesized in good yields with high chemo-, regio-, and stereoselectivities under mild conditions.

  5. Toward Efficient Palladium-Catalyzed Allylic C-H Alkylation

    DEFF Research Database (Denmark)

    Jensen, Thomas; Fristrup, Peter

    2009-01-01

    Recent breakthroughs have proved that direct palladium (II)-catalyzed allylic C-H alkylation can be achieved. This new procedure shows that the inherent requirement for a leaving group in the Tsuji-Trost palladium-catalyzed allylic alkylation can be lifted. These initial reports hold great promise...... for the development of allylic C-H alkylation into a widely applicable methodology, thus providing a means to enhance synthetic efficiency in these reactions....

  6. Palladium-Catalyzed alpha-Arylation of Tetramic Acids

    DEFF Research Database (Denmark)

    Storgaard, Morten; Dorwald, F. Z.; Peschke, B.

    2009-01-01

    A mild, racemization-free, palladium-Catalyzed alpha-arylation of tetramic acids (2,4-pyrrolidinediones) has been developed. Various amino acid-derived tetramic acids were cleanly arylated by treatment with 2 mol % of Pd(OAc)(2), 4 mol % of a sterically demanding biaryl phosphine, 2.3 equiv of K2CO...... no effect on their reactivity: both electron-rich and electron-poor aryl chlorides and bromides or triflates led to good yields. Ortho-substituted aryl halides and heteroaryl halides, however, did not undergo the title reaction....

  7. Synthesis of pyrrolo(2,3-b)quinolines by palladium-catalyzed heteroannulation

    International Nuclear Information System (INIS)

    Gee, Moon Bae; Lee, Won Jung; Yum, Eul Kgun

    2003-01-01

    Palladium-catalyzed heteroannulation of 2-amino-3-iodoquinoline derivatives and 1-trimethylsilyl internal alkynes provided highly regioselective pyrrolo(2,3-b)quinolines with trimethylsilyl group next to the nitrogen atom in the pyrrole ring

  8. Development of chiral terminal-alkene-phosphine hybrid ligands for palladium-catalyzed asymmetric allylic substitutions.

    Science.gov (United States)

    Liu, Zhaoqun; Du, Haifeng

    2010-07-02

    A variety of novel chiral terminal-alkene-phosphine hybrid ligands were successfully developed from diethyl L-tartrate for palladium-catalyzed asymmetric allylic alkylations, etherifications, and amination to give the desired products in excellent yields and ee's.

  9. Preparation of fluorinated biaryls through direct palladium-catalyzed coupling of polyfluoroarenes with aryltrifluoroborates

    KAUST Repository

    Fang, Xin; Huang, Yuanyuan; Chen, Xiaoqing; Lin, Xiaoxi; Bai, Zhengshuai; Huang, Kuo-Wei; Yuan, Yaofeng; Weng, Zhiqiang

    2013-01-01

    The direct palladium-catalyzed coupling of polyfluoroarenes with aryltrifluoroborates gave the desired products of fluorinated biaryls in good to excellent yields. A diverse set of important functional groups including methoxy, aldehyde, ester

  10. Development of a second generation palladium-catalyzed cycloalkenylation and its application to bioactive natural product synthesis.

    Science.gov (United States)

    Toyota, Masahiro

    2013-07-01

    A novel palladium-catalyzed intramolecular oxidative alkylation of unactivated olefins is described. This protocol was devised to solve one of the drawbacks of the original palladium-catalyzed cycloalkenylation that we developed. We call this new procedure the 'second generation palladium-catalyzed cycloalkenylation'. This protocol has been applied to the total syntheses of cis-195A, trans-195A, boonein, scholareins A, C, D, and alpha-skytanthine.

  11. Chalcogen-containing oxazolines in the palladium-catalyzed asymmetric allylic alkylation

    Directory of Open Access Journals (Sweden)

    Braga Antonio L.

    2006-01-01

    Full Text Available A comparative study about the ability of chiral chalcogen-containing oxazolines to act as chiral ligands in the palladium-catalyzed allylic alkylation of rac-1,3-diphenyl-2-propenyl acetate with dimethyl malonate is reported. Differences in the catalytic performance are observed with sulfur, selenium and tellurium analogues.

  12. Palladium-catalyzed aerobic oxidative cross-coupling of arylhydrazines with terminal alkynes.

    Science.gov (United States)

    Zhao, Yingwei; Song, Qiuling

    2015-09-04

    The palladium-catalyzed Sonogashira-type aerobic oxidative coupling of arylhydrazines with terminal alkynes via C-N bond cleavage has been developed; internal alkynes were afforded with a broad substrate scope. This reaction proceeds under copper- and base-free conditions with molecular oxygen as the sole oxidant and nitrogen and water as the only by-products.

  13. Practical and General Palladium-Catalyzed Synthesis of Ketones from Internal Olefins

    KAUST Repository

    Morandi, Bill; Wickens, Zachary K.; Grubbs, Robert H.

    2013-01-01

    Make it simple! A convenient and general palladium-catalyzed oxidation of internal olefins to ketones is reported. The transformation occurs at room temperature and shows wide substrate scope. Applications to the oxidation of seed-oil derivatives and a bioactive natural product (see scheme) are described, as well as intriguing mechanistic features.

  14. Practical and General Palladium-Catalyzed Synthesis of Ketones from Internal Olefins

    KAUST Repository

    Morandi, Bill

    2013-01-16

    Make it simple! A convenient and general palladium-catalyzed oxidation of internal olefins to ketones is reported. The transformation occurs at room temperature and shows wide substrate scope. Applications to the oxidation of seed-oil derivatives and a bioactive natural product (see scheme) are described, as well as intriguing mechanistic features.

  15. Preparation of fluorinated biaryls through direct palladium-catalyzed coupling of polyfluoroarenes with aryltrifluoroborates

    KAUST Repository

    Fang, Xin

    2013-07-01

    The direct palladium-catalyzed coupling of polyfluoroarenes with aryltrifluoroborates gave the desired products of fluorinated biaryls in good to excellent yields. A diverse set of important functional groups including methoxy, aldehyde, ester, nitro and halide can be well tolerated in the protocol. © 2013 Elsevier B.V. All rights reserved.

  16. Synthesis of Nitriles via Palladium-Catalyzed Water Shuffling from Amides to Acetonitrile

    OpenAIRE

    Zhang, Wandi; Haskins, Christopher W.; Yang, Yang; Dai, Mingji

    2014-01-01

    Palladium-catalyzed synthesis of nitriles from amides has been described. Two similar, but complementary reaction conditions have been identified to convert various amides including α,β,γ,δ-unsaturated amides, cinnamides, aromatic amides and alkyl amides to the corresponding nitriles in good to excellent yield.

  17. Synthesis of nitriles via palladium-catalyzed water shuffling from amides to acetonitrile.

    Science.gov (United States)

    Zhang, Wandi; Haskins, Christopher W; Yang, Yang; Dai, Mingji

    2014-12-07

    Palladium-catalyzed synthesis of nitriles from amides has been described. Two similar, but complementary reaction conditions have been identified to convert various amides including α,β,γ,δ-unsaturated amides, cinnamides, aromatic amides and alkyl amides to the corresponding nitriles in good to excellent yield.

  18. A Palladium-Catalyzed Vinylcyclopropane (3 + 2) Cycloaddition Approach to the Melodinus Alkaloids

    KAUST Repository

    Goldberg, Alexander F. G.

    2011-08-19

    A palladium-catalyzed (3+2) cycloaddition of a vinylcyclopropane and a β-nitrostyrene is employed to rapidly assemble the cyclopentane core of the Melodinus alkaloids. The ABCD ring system of the natural product family is prepared in six steps from commercially available materials.

  19. Synthesis of phenanthridines via palladium-catalyzed picolinamide-directed sequential C–H functionalization

    Directory of Open Access Journals (Sweden)

    Ryan Pearson

    2013-05-01

    Full Text Available We report a new synthesis of phenanthridines based on palladium-catalyzed picolinamide-directed sequential C–H functionalization reactions starting from readily available benzylamine and aryl iodide precursors. Under the catalysis of Pd(OAc2, the ortho-C–H bond of benzylpicolinamides is first arylated with an aryl iodide. The resulting biaryl compound is then subjected to palladium-catalyzed picolinamide-directed intramolecular dehydrogenative C–H amination with PhI(OAc2 oxidant to form the corresponding cyclized dihydrophenanthridines. The benzylic position of these dihydrophenanthridines could be further oxidized with Cu(OAc2, removing the picolinamide group and providing phenathridine products. The cyclization and oxidation could be carried out in a single step and afford phenathridines in moderate to good yields.

  20. Palladium-catalyzed aryl C-H olefination with unactivated, aliphatic alkenes.

    Science.gov (United States)

    Deb, Arghya; Bag, Sukdev; Kancherla, Rajesh; Maiti, Debabrata

    2014-10-01

    Palladium-catalyzed coupling between aryl halides and alkenes (Mizoroki-Heck reaction) is one of the most popular reactions for synthesizing complex organic molecules. The limited availability, problematic synthesis, and higher cost of aryl halide precursors (or their equivalents) have encouraged exploration of direct olefination of aryl carbon-hydrogen (C-H) bonds (Fujiwara-Moritani reaction). Despite significant progress, the restricted substrate scope, in particular noncompliance of unactivated aliphatic olefins, has discouraged the use of this greener alternative. Overcoming this serious limitation, we report here a palladium-catalyzed chelation-assisted ortho C-H bond olefination of phenylacetic acid derivatives with unactivated, aliphatic alkenes in good to excellent yields with high regio- and stereoselectivities. The versatility of this operationally simple method has been demonstrated through drug diversification and sequential C-H olefination for synthesizing divinylbenzene derivatives.

  1. Palladium-catalyzed, asymmetric Baeyer–Villiger oxidation of prochiral cyclobutanones with PHOX ligands

    KAUST Repository

    Petersen, Kimberly S.

    2011-06-01

    Described in this report is a general method for the conversion of prochiral 3-substituted cyclobutanones to enantioenriched γ-lactones through a palladium-catalyzed Baeyer-Villiger oxidation using phosphinooxazoline ligands in up to 99% yield and 81% ee. Lactones of enantiopurity ≥93% could be obtained through a single recrystallization step. Importantly, 3,3-disubtituted cyclobutanones produced enantioenriched lactones containing a β-quaternary center. © 2011 Elsevier Ltd. All rights reserved.

  2. Novel Role of Carbon Dioxide as a Selective Agent in Palladium-Catalyzed Cyclotrimerization of Alkynes

    Institute of Scientific and Technical Information of China (English)

    李金恒; 谢叶香

    2004-01-01

    Carbon dioxide was found as a selective agent to promote the palladium-catalyzed cyclotrimerization of alkynes in water. Both aryl and alkylacetylenes afforded the corresponding cyclotrimerization products regioselectively in high yields using PdCl2, CuCl2, and CO2 as the catalytic system. However, tert-butylacetylene bearing a bulky group gave a dimerization product. Mechanism of this reaction was also discussed.

  3. Palladium-Catalyzed Carbenylative Cross-Coupling and Carbenylative Amination Utilizing Vinylcarbenes

    OpenAIRE

    Agee, Christopher

    2017-01-01

    This work focuses on the use of N-tosylhydrazones derived from α,β-unsaturated aldehydes – precursors to vinylcarbene ligands – in palladium-catalyzed carbenylative cross-coupling and carbenylative amination reactions. These carbenylative reactions were used to form η3-allylpalladium intermediates that generate stereogenic centers at the carbene center. An initial acyclic model system was used to intercept a well-known prochiral 1,3-diphenylallyl intermediate to probe the feasibility of enant...

  4. Palladium catalyzed selective distal C-H olefination of biaryl systems.

    Science.gov (United States)

    Maity, Soham; Hoque, Ehtasimul; Dhawa, Uttam; Maiti, Debabrata

    2016-11-29

    Palladium catalyzed selective distal C-H activation with nitrile based templates has been of significant research interest in recent times. In this report, we disclose the distal C-H olefination of biphenyl systems with high regio- and stereo-selectivity and useful synthetic yields. The utility of this method has been demonstrated through its wide olefin scope, its operation at the gram scale and the easy removal/recovery of the directing group.

  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

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

  6. Mild Palladium Catalyzed ortho C-H Bond Functionalizations of Aniline Derivatives.

    Science.gov (United States)

    Tischler, Ms Orsolya; Tóth, Mr Balázs; Novák, Zoltán

    2017-02-01

    This account collects the developments and transformations which avoid the utilization of harsh reaction conditions in the field of palladium catalyzed, ortho-directed C-H activation of aniline derivatives from the first attempts to up-to-date results, including the results of our research laboratory. The discussed functionalizations performed under mild conditions include acylation, olefination, arylation, alkylation, alkoxylation reactions. Beside the optimization studies and the synthetic applications mechanistic investigations are also presented. © 2017 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Directory of Open Access Journals (Sweden)

    Katrina Tait

    2016-10-01

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

  8. Scope and mechanism in palladium-catalyzed isomerizations of highly substituted allylic, homoallylic, and alkenyl alcohols.

    Science.gov (United States)

    Larionov, Evgeny; Lin, Luqing; Guénée, Laure; Mazet, Clément

    2014-12-03

    Herein we report the palladium-catalyzed isomerization of highly substituted allylic alcohols and alkenyl alcohols by means of a single catalytic system. The operationally simple reaction protocol is applicable to a broad range of substrates and displays a wide functional group tolerance, and the products are usually isolated in high chemical yield. Experimental and computational mechanistic investigations provide complementary and converging evidence for a chain-walking process consisting of repeated migratory insertion/β-H elimination sequences. Interestingly, the catalyst does not dissociate from the substrate in the isomerization of allylic alcohols, whereas it disengages during the isomerization of alkenyl alcohols when additional substituents are present on the alkyl chain.

  9. Palladium-Catalyzed Tandem Oxidative Arylation/Olefination of Aromatic Tethered Alkenes/Alkynes.

    Science.gov (United States)

    Gao, Yang; Gao, Yinglan; Wu, Wanqing; Jiang, Huanfeng; Yang, Xiaobo; Liu, Wenbo; Li, Chao-Jun

    2017-01-18

    We describe herein a palladium-catalyzed tandem oxidative arylation/olefination reaction of aromatic tethered alkenes/alkynes for the synthesis of dihydrobenzofurans and 2 H-chromene derivatives. This reaction features a 1,2-difunctionalization of C-C π-bond with two C-H bonds using O 2 as terminal oxidant at room temperature. The products obtained are valuable synthons and important scaffolds in biological agents and natural products. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Mechanism of the palladium-catalyzed hydrothiolation of alkynes to thioethers: a DFT study.

    Science.gov (United States)

    Zhang, Xing-hui; Geng, Zhi-yuan; Wang, Ke-tai; Li, Shan-shan

    2014-09-01

    The mechanisms of the palladium-catalyzed hydrothiolation of alkynes with thiols were investigated using density functional theory at the B3LYP/6-31G(d, p) (SDD for Pd) level. Solvent effects on these reactions were explored using the polarizable continuum model (PCM) for the solvent tetrahydrofuran (THF). Markovnikov-type vinyl sulfides or cis-configured anti-Markovnikov-type products were formed by three possible pathways. Our calculation results suggested the following: (1) the first step of the cycle is a proton-transfer process from thiols onto the palladium atom to form a palladium-thiolate intermediate. The palladium-thiolate species is attacked on alkynes to obtain an elimination product, liberating the catalyst. (2) The higher activation energies for the alkyne into the palladium-thiolate bond indicate that this step is the rate-determining step. The Markovnikov-type vinyl sulfide product is favored. However, for the aromatic alkyne, the cis-configured anti-Markovnikov-type product is favored. (3) The activation energy would reduce when thiols are substituted with an aromatic group. Our calculated results are consistent with the experimental observations of Frech and colleagues for the palladium-catalyzed hydrothiolation of alkynes to thiols.

  11. Palladium-catalyzed three-component reaction of N-tosyl hydrazones, isonitriles and amines leading to amidines.

    Science.gov (United States)

    Dai, Qiang; Jiang, Yan; Yu, Jin-Tao; Cheng, Jiang

    2015-12-04

    A palladium-catalyzed three-component reaction between N-tosyl hydrazones, aryl isonitriles and amines was developed, leading to amidines in moderate to good yields. This procedure features the rapid construction of amidine frameworks with high diversity and complexity. Ketenimines serve as intermediates, which encounter nucleophilic attack by amines to produce amidines.

  12. Palladium-catalyzed domino C,N-coupling/carbonylation/Suzuki coupling reaction: an efficient synthesis of 2-aroyl-/heteroaroylindoles.

    Science.gov (United States)

    Arthuis, Martin; Pontikis, Renée; Florent, Jean-Claude

    2009-10-15

    A convenient one-pot synthesis of 2-aroylindoles using a domino palladium-catalyzed C,N-coupling/carbonylation/C,C-coupling sequence is described. The reaction involved easily prepared 2-gem-dibromovinylanilines and boronic acids under carbon monoxide. Optimized reaction conditions allowed the construction of a wide variety of highly functionalized 2-aroyl-/heteroaroylindoles in satisfactory yields.

  13. Sulfonium Salts as Alkylating Agents for Palladium-Catalyzed Direct Ortho Alkylation of Anilides and Aromatic Ureas.

    Science.gov (United States)

    Simkó, Dániel Cs; Elekes, Péter; Pázmándi, Vivien; Novák, Zoltán

    2018-02-02

    A novel method for the ortho alkylation of acetanilide and aromatic urea derivatives via C-H activation was developed. Alkyl dibenzothiophenium salts are considered to be new reagents for the palladium-catalyzed C-H activation reaction, which enables the transfer of methyl and other alkyl groups from the sulfonium salt to the aniline derivatives under mild catalytic conditions.

  14. Palladium-Catalyzed C-H Functionalization Using Guanidine as a Directing Group: Ortho Arylation and Olefination of Arylguanidines

    Science.gov (United States)

    Shao, Jiaan; Chen, Wenteng; Giulianotti, Marc A.; Houghten, Richard A.; Yu, Yongping

    2012-01-01

    Palladium-catalyzed C-H functionalization using guanidine as the directing group was achieved under mild reaction conditions. Various guanidine derivatives were produced in moderate to good yields by using simple unactivated arenes or ethyl acrylate as the source of arylation or olefination respectively. PMID:23095022

  15. Palladium-catalyzed C-H olefination of uracils and caffeines using molecular oxygen as the sole oxidant.

    Science.gov (United States)

    Zhang, Xinyu; Su, Lv; Qiu, Lin; Fan, Zhenwei; Zhang, Xiaofeng; Lin, Shen; Huang, Qiufeng

    2017-04-18

    The palladium-catalyzed oxidative C-H olefination of uracils or caffeines with alkenes using an atmospheric pressure of molecular oxygen as the sole oxidant has been disclosed. This novel strategy offers an efficient and environmentally friendly method to biologically important C5-alkene uracil derivatives or C8-alkene caffeine derivatives.

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

    KAUST Repository

    Ebner, Davidâ C.

    2009-12-07

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

  17. Synthesis of heterocyclic compounds through palladium-catalyzed C-H cyclization processes.

    Science.gov (United States)

    Inamoto, Kiyofumi

    2013-01-01

    Herein, we describe our development of synthetic methods for heterocyclic compounds based on the palladium-catalyzed carbon-hydrogen bond (C-H) functionalization/intramolecular carbon-heteroatom (nitrogen or sulfur) bond formation process. By this C-H cyclization method, we efficiently prepared various N-heterocycles, including indazoles, indoles, and 2-quinolinones, as well as S-heterocycles such as benzothiazoles and benzo[b]thiophenes. Yields are typically good to high and good functional-group tolerance is observed for each process, thereby indicating that the method provides a novel, highly applicable synthetic route to the abovementioned biologically important heterocyclic frameworks. As an application of this approach, an auto-tandem-type, one-pot process involving the oxidative Heck reaction and subsequent C-H cyclization using cinnamamides and arylboronic acids as starting materials in the presence of a palladium catalyst was also developed for the rapid construction of the 2-quinolinone nucleus.

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

    KAUST Repository

    Ebner, Davidâ C.; Bagdanoff, Jeffreyâ T.; Ferreira, Ericâ M.; McFadden, Ryanâ M.; Caspi, Danielâ D.; Trend, Raissaâ M.; Stoltz, Brianâ M.

    2009-01-01

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

  19. Stereoselective synthesis of tricyclic compounds by intramolecular palladium-catalyzed addition of aryl iodides to carbonyl groups

    Directory of Open Access Journals (Sweden)

    Jakub Saadi

    2016-06-01

    Full Text Available Starting from γ-ketoesters with an o-iodobenzyl group we studied a palladium-catalyzed cyclization process that stereoselectively led to bi- and tricyclic compounds in moderate to excellent yields. Four X-ray crystal structure analyses unequivocally defined the structure of crucial cyclization products. The relative configuration of the precursor compounds is essentially transferred to that of the products and the formed hydroxy group in the newly generated cyclohexane ring is consistently in trans-arrangement with respect to the methoxycarbonyl group. A transition-state model is proposed to explain the observed stereochemical outcome. This palladium-catalyzed Barbier-type reaction requires a reduction of palladium(II back to palladium(0 which is apparently achieved by the present triethylamine.

  20. Palladium-Catalyzed ortho-Olefination of Phenyl Acetic and Phenyl Propylacetic Esters via C-H Bond Activation.

    Science.gov (United States)

    Hu, Jundie; Guan, Mingyu; Han, Jian; Huang, Zhi-Bin; Shi, Da-Qing; Zhao, Yingsheng

    2015-08-21

    A highly regioselective palladium-catalyzed ester-directed ortho-olefination of phenyl acetic and propionic esters with olefins via C-H bond activation has been developed. A wide variety of phenyl acetic and propionic esters were tolerated in this transformation, affording the corresponding olefinated aromatic compounds. The ortho-olefination of heterocyclic acetic and propionic esters also took place smoothly giving the products in good yields, thus proving the potential utility of this protocol in synthetic chemistry.

  1. Palladium-catalyzed hydrodehalogenation of 1,2,4,5-tetrachlorobenzene in water-ethanol mixtures

    Energy Technology Data Exchange (ETDEWEB)

    Wee, Hun-Young [Department of Civil Engineering, Texas A and M University, College Station, TX 77843 (United States); Cunningham, Jeffrey A. [Department of Civil and Environmental Engineering, University of South Florida, Tampa, FL 33620 (United States)], E-mail: cunning@eng.usf.edu

    2008-06-30

    Palladium-catalyzed hydrodehalogenation (HDH) was applied for destroying 1,2,4,5-tetrachlorobenzene (TeCB) in mixtures of water and ethanol. This investigation was performed as a critical step in the development of a new technology for clean-up of soil contaminated by halogenated hydrophobic organic contaminants. The main goals of the investigation were to demonstrate the feasibility of the technology, to determine the effect of the solvent composition (water:ethanol ratio), and to develop a model for the kinetics of the dehalogenation process. All experiments were conducted in a batch reactor at ambient temperature under mild hydrogen pressure. The experimental results are all consistent with a Langmuir-Hinshelwood model for heterogeneous catalysis. Major findings that can be interpreted within the Langmuir-Hinshelwood framework include: (1) the rate of hydrodehalogenation depends strongly on the solvent composition, increasing as the water fraction of the solvent increases; (2) the HDH rate increases as the catalyst concentration in the reactor increases; (3) when enough catalyst is present, the HDH reaction appears to follow first-order kinetics, but the kinetics appear to be zero-order at low catalyst concentrations. TeCB is converted rapidly and quantitatively to benzene, with only trace concentrations of 1,2,4-trichlorobenzene appearing as a reactive intermediate. The results obtained here have important implications for the further development of the proposed soil remediation technology, and may also be important for the treatment of other hazardous waste streams.

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

    Directory of Open Access Journals (Sweden)

    Masato Ohashi

    2014-09-01

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

  3. Palladium-catalyzed hydrodehalogenation of 1,2,4,5-tetrachlorobenzene in water-ethanol mixtures

    International Nuclear Information System (INIS)

    Wee, Hun-Young; Cunningham, Jeffrey A.

    2008-01-01

    Palladium-catalyzed hydrodehalogenation (HDH) was applied for destroying 1,2,4,5-tetrachlorobenzene (TeCB) in mixtures of water and ethanol. This investigation was performed as a critical step in the development of a new technology for clean-up of soil contaminated by halogenated hydrophobic organic contaminants. The main goals of the investigation were to demonstrate the feasibility of the technology, to determine the effect of the solvent composition (water:ethanol ratio), and to develop a model for the kinetics of the dehalogenation process. All experiments were conducted in a batch reactor at ambient temperature under mild hydrogen pressure. The experimental results are all consistent with a Langmuir-Hinshelwood model for heterogeneous catalysis. Major findings that can be interpreted within the Langmuir-Hinshelwood framework include: (1) the rate of hydrodehalogenation depends strongly on the solvent composition, increasing as the water fraction of the solvent increases; (2) the HDH rate increases as the catalyst concentration in the reactor increases; (3) when enough catalyst is present, the HDH reaction appears to follow first-order kinetics, but the kinetics appear to be zero-order at low catalyst concentrations. TeCB is converted rapidly and quantitatively to benzene, with only trace concentrations of 1,2,4-trichlorobenzene appearing as a reactive intermediate. The results obtained here have important implications for the further development of the proposed soil remediation technology, and may also be important for the treatment of other hazardous waste streams

  4. A tandem Mannich addition–palladium catalyzed ring-closing route toward 4-substituted-3(2H-furanones

    Directory of Open Access Journals (Sweden)

    Jubi John

    2014-06-01

    Full Text Available A facile route towards highly functionalized 3(2H-furanones via a sequential Mannich addition–palladium catalyzed ring closing has been elaborated. The reaction of 4-chloroacetoacetate esters with imines derived from aliphatic and aromatic aldehydes under palladium catalysis afforded 4-substituted furanones in good to excellent yields. 4-Hydrazino-3(2H-furanones could also be synthesized from diazo esters in excellent yields by utilising the developed strategy. We could also efficiently transform the substituted furanones to aza-prostaglandin analogues.

  5. Palladium-catalyzed cyclization reactions of 2-vinylthiiranes with heterocumulenes. Regioselective and enantioselective formation of thiazolidine, oxathiolane, and dithiolane derivatives.

    Science.gov (United States)

    Larksarp, C; Sellier, O; Alper, H

    2001-05-18

    The first palladium-catalyzed ring-expansion reaction of 2-vinylthiiranes with heterocumulenes to form sulfur-containing five-membered-ring heterocycles is described. This regioselective reaction requires 5 mol % of Pd(2)(dba)(3).CHCl(3) and 10 mol % of bidendate phosphine ligand (dppp, BINAP), at 50-80 degrees C, in THF. The reaction of 2-vinylthiiranes with carbodiimides, isocyanates, and ketenimines affords 1,3-thiazolidine derivatives, whereas the reaction with diphenylketene or isothiocyanates results in the formation of 1,3-oxathiolane or 1,3-dithiolane compounds in good to excellent isolated yields and in up to 78% ee.

  6. Palladium-Catalyzed Synthesis of Natural and Unnatural 2-, 5-, and 7-Oxygenated Carbazole Alkaloids from N-Arylcyclohexane Enaminones

    Directory of Open Access Journals (Sweden)

    Joaquín Tamariz

    2013-08-01

    Full Text Available A palladium-catalyzed synthesis of the carbazole framework is described, including the preparation of 2-, 5-, and 7-oxygenated natural and unnatural carbazole alkaloids. A series of N-arylcyclohexane enaminones, generated by condensation of cyclohexane-1,3-dione with diverse anilines, were aromatized by a Pd(0-catalyzed thermal treatment to afford the corresponding diarylamines. The latter were submitted to a Pd(II-catalyzed cyclization and methylation processes to provide the desired carbazoles, including clausine V. Following an inverse strategy, a new and short total synthesis of glycoborine is also reported.

  7. Palladium-catalyzed heteroannulation approach to 7-azatryptophan with a Schöllkopf chiral auxiliary

    Energy Technology Data Exchange (ETDEWEB)

    Gee, Moon Bae; Kim, Tae Seung; Yun, Eul Kgun [Dept. of Chemistry, Chungnam National University, Daejeon (Korea, Republic of)

    2015-05-15

    Our previous results on heteroannulation with unprotected 2-amino-3-iodopyridine and internal alkynes showed very low yields of the annulated product. The synthetic limitation could be due to the low nucleophilicity of the nitrogen that exists in the three tautomeric forms of 2-amino-pyridine (Scheme 1) or to the easy formation of a palladium complex with 2-aminopyridine. First, we examined the synthesis of the azaindole precursor, followed by reaction with a Schöllkopf chiral auxiliary. The heteroannulation provided the desired annulated product 5 in 60% yield, along with an uncyclized Sonogawasihra coupling product. After purifying product 5 by column chromatography, it was converted to 7-aza-tryptophan.

  8. Pyrazine-functionalized calix[4]arenes: synthesis by palladium-catalyzed cross-coupling with phosphorus pronucleophiles and metal ion extraction properties

    NARCIS (Netherlands)

    Nikishkin, N.; Huskens, Jurriaan; Ansari, S.A.; Mohapatra, P.K.; Verboom, Willem

    2013-01-01

    A series of pyrazine-based calix[4]arene extractants was prepared by a stepwise functionalization, comprising palladium-catalyzed exhaustive cross-coupling of di- and tetrasubstituted calix[4]arenes bearing chloropyrazine moieties. The extraction behavior of the synthesized ligands was studied on

  9. Palladium-Catalyzed Atom-Transfer Radical Cyclization at Remote Unactivated C(sp3 )-H Sites: Hydrogen-Atom Transfer of Hybrid Vinyl Palladium Radical Intermediates.

    Science.gov (United States)

    Ratushnyy, Maxim; Parasram, Marvin; Wang, Yang; Gevorgyan, Vladimir

    2018-03-01

    A novel mild, visible-light-induced palladium-catalyzed hydrogen atom translocation/atom-transfer radical cyclization (HAT/ATRC) cascade has been developed. This protocol involves a 1,5-HAT process of previously unknown hybrid vinyl palladium radical intermediates, thus leading to iodomethyl carbo- and heterocyclic structures. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Palladium-catalyzed cyclocarbonylation of o-iodoanilines with heterocumulenes: regioselective preparation of 4(3H)-quinazolinone derivatives

    Science.gov (United States)

    Larksarp; Alper

    2000-05-09

    A catalyst system comprising palladium acetate-bidentate phosphine is effective for the cyclocarbonylation of o-iodoanilines with heterocumulenes at 70-100 degrees C for 12-24 h to give the corresponding 4(3H)-quinazolinone derivatives in good yields. Utilizing o-iodoaniline with isocyanates, carbodiimides, and ketenimines for the reaction, 2,4-(1H,3H)-quinazolinediones, 2-amino-4(3H)-quinazolinones and 2-alkyl-4(3H)-quinazolinones were obtained, respectively. The nature of the substrates including the electrophilicity of the carbon center of the carbodiimide, and the stability of the ketenimine, influence the product yields of this reaction. Urea-type intermediates are believed to be generated first in situ from the reaction of o-iodoanilines with heterocumulenes, followed by palladium-catalyzed carbonylation and cyclization to yield the products.

  11. Palladium-Catalyzed Asymmetric Allylic Alkylation of 4-Substituted Isoxazolidin-5-ones: Straightforward Access to β2,2 -Amino Acids.

    Science.gov (United States)

    Nascimento de Oliveira, Marllon; Arseniyadis, Stellios; Cossy, Janine

    2018-04-03

    We report here an unprecedented and highly enantioselective palladium-catalyzed allylic alkylation applied to 4-substituted isoxazolidin-5-ones. Ultimately, the process provides a straightforward access to β 2,2 -amino acids bearing an all-carbon quaternary stereogenic center in great yields and a high degree of enantioselectivity. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Synthesis of Conjugated Small Molecules and Polymers by a Palladium Catalyzed Cyclopentannulation Strategy: Towards New Organic Semiconductors

    Science.gov (United States)

    Bheemireddy, Sambasiva Reddy

    The utility of conjugated small molecules and polymers as organic semiconductors have seen a tremendous growth in research and development in academia as well as industry because of their processability and flexibility advantages in comparison to inorganic semiconductors. The extensive research over the years has produced a large number of p-type (hole conducting) and n-type (electron conducting) semiconductors that can be used to construct organic electronic devices. Of these materials, p-type semiconductors are more established and extensively studied because of the ease of preparation as well as their better general stability in comparison to n-type materials. Despite recent research into the development of n-type materials, fullerene (C60 and C 70) and its derivatives are still the predominant materials used as electron acceptors for OPV applications. By taking advantage of the electron accepting behavior of cyclopenta[hi]aceanthrylene fragment of C70, we have designed and synthesized new materials based on cyclopenta-fused polycyclic aromatic hydrocarbons (CP-PAHs). By using a newly developed palladium catalyzed cyclopentannulation methodology, 1,2,6,7- tetraarylcyclopenta[hi]aceanthrylenes were prepared by treating diarylethynylenes with 9,10-dibromoanthracene. Scholl cyclodehydrogenation was used to close the externally fused aryl groups to provide access to contorted 2,7,13,18- tetraalkoxytetrabenzo[f,h,r,t]rubicenes. The contortion provides access to more soluble materials than their planar counterparts but still ii allows significant pi-pi stacking between molecules. Using a modified palladium catalyzed cyclopentannulation polymerization followed by a cyclodehydrogenation reaction, a nonconventional synthesis of CP-PAH embedded ladder polymers was also achieved. These ladder polymers possess broad UV-Vis absorptions and narrow optical gaps of 1.17-1.29 eV. The synthesis of new donor-acceptor copolymers incorporating electron accepting 1,2,6,7- tetra(4

  13. Atroposelective Synthesis of Axially Chiral Biaryls by Palladium-Catalyzed Asymmetric C-H Olefination Enabled by a Transient Chiral Auxiliary.

    Science.gov (United States)

    Yao, Qi-Jun; Zhang, Shuo; Zhan, Bei-Bei; Shi, Bing-Feng

    2017-06-01

    Atroposelective synthesis of axially chiral biaryls by palladium-catalyzed C-H olefination, using tert-leucine as an inexpensive, catalytic, and transient chiral auxiliary, has been realized. This strategy provides a highly efficient and straightforward access to a broad range of enantioenriched biaryls in good yields (up to 98 %) with excellent enantioselectivities (95 to >99 % ee). Kinetic resolution of trisubstituted biaryls bearing sterically more demanding substituents is also operative, thus furnishing the optically active olefinated products with excellent selectivity (95 to >99 % ee, s-factor up to 600). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Scope and Limitations of Auxiliary-Assisted, Palladium-Catalyzed Arylation and Alkylation of sp2 and sp3 C-H Bonds

    Science.gov (United States)

    Nadres, Enrico T.; Santos, Gerson Ivan Franco; Shabashov, Dmitry; Daugulis, Olafs

    2013-01-01

    The scope of palladium-catalyzed, auxiliary-assisted direct arylation and alkylation of sp2 and sp3 C-H bonds of amine and carboxylic acid derivatives has been investigated. The method employs a palladium acetate catalyst, substrate, aryl, alkyl, benzyl, or allyl halide, and inorganic base in t-amyl alcohol or water solvent at 100-140 °C. Aryl and alkyl iodides as well as benzyl and allyl bromides are competent reagents in this transformation. Picolinic acid auxiliary is used for amine γ-functionalization and 8-aminoquinoline auxiliary is used for carboxylic acid β-functionalization. Some optimization of base, additives, and solvent is required for achieving best results. PMID:24090404

  15. Palladium-catalyzed regio- and stereoselective cross-addition of terminal alkynes to ynol ethers and synthesis of 1,4-enyn-3-ones.

    Science.gov (United States)

    Babu, Madala Hari; Dwivedi, Vikas; Kant, Ruchir; Reddy, Maddi Sridhar

    2015-03-16

    Conjugated enynes, enol ethers, and enynones are versatile building blocks that can be elaborated by a wide variety of synthetic transformations. The selective synthesis of such units is a prerequisite for their effective utilization. The synthesis of conjugated 2-phenoxyenynes through a palladium-catalyzed cross-addition of terminal alkynes to phenylethynyl ethers (hydroalkynylation) is now presented. The reaction is highly regio-, stereo-, and chemoselective, and shows excellent tolerance toward functional groups. The addition further features very mild reaction conditions (room temperature) and an inexpensive catalytic system (without a ligand and with a cheaply available Pd catalyst). The thus synthesized enynyl ethers with allylic hydroxy tethers, which survived the reaction, were shown to be ready precursors for valuable 1-en-4-yn-3-ones. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Detailed Mechanistic Studies on Palladium-Catalyzed Selective C-H Olefination with Aliphatic Alkenes: A Significant Influence of Proton Shuttling.

    Science.gov (United States)

    Deb, Arghya; Hazra, Avijit; Peng, Qian; Paton, Robert S; Maiti, Debabrata

    2017-01-18

    Directing group-assisted regioselective C-H olefination with electronically biased olefins is well studied. However, the incorporation of unactivated olefins has remained largely unsuccessful. A proper mechanistic understanding of olefination involving unactivated alkenes is therefore essential for enhancing their usage in future. In this Article, detailed experimental and computational mechanistic studies on palladium catalyzed C-H olefination with unactivated, aliphatic alkenes are described. The isolation of Pd(II) intermediates is shown to be effective for elucidating the elementary steps involved in catalytic olefination. Reaction rate and order determination, control experiments, isotopic labeling studies, and Hammett analysis have been used to understand the reaction mechanism. The results from these experimental studies implicate β-hydride elimination as the rate-determining step and that a mechanistic switch occurs between cationic and neutral pathway. Computational studies support this interpretation of the experimental evidence and are used to uncover the origins of selectivity.

  17. A Recyclable Palladium-Catalyzed Synthesis of 2-Methylene-2,3-Dihydrobenzofuran-3-ols by Cycloisomerization of 2-(1-Hydroxyprop-2-ynylphenols in Ionic Liquids

    Directory of Open Access Journals (Sweden)

    Bartolo Gabriele

    2013-09-01

    Full Text Available A recyclable palladium-catalyzed synthesis of 2-methylene-2,3-dihydrobenzofuran-3-ols 2 by heterocyclization of 2-(1-hydroxyprop-2-ynylphenols 1 in an ionic liquid medium (BmimBF4 is presented. The process takes place under relatively mild conditions (100 °C, 5 h in the presence of catalytic amounts (2 mol % of PdI2 in conjunction with KI (5 equiv with respect to PdI2 and an organic base, such as morpholine (1 equiv with respect to 1, to give 2 in high yields (70%–86%. The PdI2-KI catalytic system could be recycled up to six times without appreciable loss of activity. Moreover, products 2 could be easily converted in a one-pot fashion into 2-hydroxymethylbenzofurans 3 (52%–71%, based on 1 and 2-methoxymethylbenzofurans 4 (52%–80%, based on 1 by acid-catalyzed allylic isomerization or allylic nucleophilic substitution.

  18. Palladium-catalyzed Suzuki-Miyaura coupling of amides by carbon-nitrogen cleavage: general strategy for amide N-C bond activation.

    Science.gov (United States)

    Meng, Guangrong; Szostak, Michal

    2016-06-15

    The first palladium-catalyzed Suzuki-Miyaura cross-coupling of amides with boronic acids for the synthesis of ketones by sterically-controlled N-C bond activation is reported. The transformation is characterized by operational simplicity using bench-stable, commercial reagents and catalysts, and a broad substrate scope, including substrates with electron-donating and withdrawing groups on both coupling partners, steric-hindrance, heterocycles, halides, esters and ketones. The scope and limitations are presented in the synthesis of >60 functionalized ketones. Mechanistic studies provide insight into the catalytic cycle of the cross-coupling, including the first experimental evidence for Pd insertion into the amide N-C bond. The synthetic utility is showcased by a gram-scale cross-coupling and cross-coupling at room temperature. Most importantly, this process provides a blueprint for the development of a plethora of metal catalyzed reactions of typically inert amide bonds via acyl-metal intermediates. A unified strategy for amide bond activation to enable metal insertion into N-C amide bond is outlined ().

  19. Palladium-catalyzed coupling reactions

    CERN Document Server

    Molnár, Árpád

    2013-01-01

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

  20. Palladium-catalyzed Reppe carbonylation.

    Science.gov (United States)

    Kiss, G

    2001-11-01

    PdX2L2/L/HA (A = weakly coordinating anion, L = phosphine) complexes are active catalysts in the hydroesterification of alkenes, alkynes, and conjugated dienes. Shell, the only major corporate player in the field, recently developed two very active catalyst systems tailored to the hydroesterification of either alkenes or alkynes. The hydroesterification of propyne with their Pd(OAc)2/PN/HA (PN = (2-pyridyl)diphenylphosphine, HA = strong acid with weakly coordinating anion, like methanesulfonic acid) catalyst has been declared commercially ready. However, despite the significant progress in the activity of Pd-hydroesterification catalysts, further improvements are warranted. Thus, for example, activity maintenance still seems to be an issue. Homogeneous Pd catalysts are prone to a number of deactivation reactions. Activity and stability promoters are often corrosive and add to the complexity of the system, making it less attractive. Nonetheless, the versatility of the process and its tolerance toward the functional groups of substrates should appeal especially to the makers of specialty products. Although hydroesterification yields esters from alkenes, alkynes, and dienes in fewer steps than hydroformylation does, the latter has some advantages at the current state of the art. (1) Hydroformylation catalysts, particularly some recently published phosphine-modified Rh systems, can achieve very high regioselectivity for the linear product that hydroesterification catalysts cannot match yet. By analogy with hydroformylation, bulkier ligands ought to be tested in hydroesterification to increase normal-ester selectivity. (2) Hydroformylation is proven, commercial. Hydroesterification can only replace it if it can provide significant economic incentives. Similar or just marginally better performance could not justify the cost of development of a new technology. (3) Hydroesterification requires pure CO while hydroformylation uses syngas, a mixture of CO and H2. The latter is typically more available and less expensive (for industrial applications CO is most often separated from syngas). (4) The acid component of the hydroesterification catalyst makes the process corrosive. It would be desirable to develop new hydroesterification catalysts that do not require acid stabilizer/activity booster. Clearly, any new hydroesterification technology will directly compete with the hydroformylation route. This is especially true for olefin feeds, since both processes add one CO to the olefin, yielding oxygenates that can be converted into identical products. For some niche applications, like the production of MMA from propyne, hydroesterification seems to have an advantage as compared to hydroformylation due to the high activity and selectivity of the Pd(OAc)2/(2-pyridyl)diphenylphosphine catalyst. Since hydroesterification is an emerging technology, it is reasonable to assume that the potential for improvement is greater than in the mature hydroformylation. It is therefore possible that hydroesterification will become competitive in the future; thus, continued effort in the field is warranted.

  1. 38 CFR 3.207 - Void or annulled marriage.

    Science.gov (United States)

    2010-07-01

    ... 38 Pensions, Bonuses, and Veterans' Relief 1 2010-07-01 2010-07-01 false Void or annulled marriage... Void or annulled marriage. Proof that a marriage was void or has been annulled should consist of: (a... marriage void, together with such other evidence as may be required for a determination. (b) Annulled. A...

  2. Arranged marriages annulled by law.

    Science.gov (United States)

    Zhu, H

    1996-06-01

    The arranged marriages of 210 young people in Yongle Town in Zunyi County of Guizhou Province were dissolved in 1995. The proportion of child betrothals, which generally happens among close relatives, is as high as 85% in the town. Some engagements, known as fetus betrothals or belt betrothals, are arranged before the children are born or while they are still infants strapped (belted) to their mothers. Dissemination of information from the Constitution, the Marriage Law, and the Regulations on the Registration of Marriage concerning marriage, healthier births, and good upbringing of children, and other information on reproductive health, has shown young people that they have the freedom to love and marry of their own free will, that their marriage is protected by law, and that consanguineous marriage is harmful to the health of future generations. Some convinced their parents that their arranged marriages should be annulled.

  3. Palladium-Catalyzed Asymmetric Quaternary Stereocenter Formation

    NARCIS (Netherlands)

    Gottumukkala, Aditya L.; Matcha, Kiran; Lutz, Martin; de Vries, Johannes G.; Minnaard, Adriaan J.

    2012-01-01

    An efficient palladium catalyst is presented for the formation of benzylic quaternary stereocenters by conjugate addition of arylboronic acids to a variety of beta,beta-disubstituted carbocyclic, heterocyclic, and acyclic enones. The catalyst is readily prepared from PdCl2, PhBOX, and AgSbF6, and

  4. Palladium-catalyzed asymmetric quaternary stereocenter formation

    NARCIS (Netherlands)

    Gottumukkala, A.L.; Matcha, K.; Lutz, M.; de Vries, J.G.; Minnaard, A.J.

    2012-01-01

    An efficient palladium catalyst is presented for the formation of benzylic quaternary stereocenters by conjugate addition of arylboronic acids to a variety of β,β-disubstituted carbocyclic, heterocyclic, and acyclic enones. The catalyst is readily prepared from PdCl2, PhBOX, and AgSbF6, and provides

  5. Palladium Catalyzed Allylic C-H Alkylation

    DEFF Research Database (Denmark)

    Engelin, Casper Junker; Fristrup, Peter

    2011-01-01

    are highlighted with emphasis on those leading to C-C bond formation, but where it was deemed necessary for the general understanding of the process closely related C-H oxidations and aminations are also included. It is found that C-H cleavage is most likely achieved by ligand participation which could involve......-H alkylation reaction which is the topic of the current review. Particular emphasis is put on current mechanistic proposals for the three reaction types comprising the overall transformation: C-H activation, nucleophillic addition, and re-oxidation of the active catalyst. Recent advances in C-H bond activation...... an acetate ion coordinated to Pd. Several of the reported systems rely on benzoquinone for re-oxidation of the active catalyst. The scope for nucleophilic addition in allylic C-H alkylation is currently limited, due to demands on pKa of the nucleophile. This limitation could be due to the pH dependence...

  6. Zirconacyclopentadiene-annulated polycyclic aromatic hydrocarbons

    International Nuclear Information System (INIS)

    Kiel, Gavin R.; Ziegler, Micah S.; Tilley, T. Don

    2017-01-01

    Syntheses of large polycyclic aromatic hydrocarbons (PAHs) and graphene nanostructures demand methods that are capable of selectively and efficiently fusing large numbers of aromatic rings, yet such methods remain scarce. Herein, we report a new approach that is based on the quantitative intramolecular reductive cyclization of an oligo(diyne) with a low-valent zirconocene reagent, which gives a PAH with one or more annulated zirconacyclopentadienes (ZrPAHs). The efficiency of this process is demonstrated by a high-yielding fivefold intramolecular coupling to form a helical ZrPAH with 16 fused rings (from a precursor with no fused rings). Several other PAH topologies are also reported. Protodemetalation of the ZrPAHs allowed full characterization (including by X-ray crystallography) of PAHs containing one or more appended dienes with the ortho-quinodimethane (o-QDM) structure, which are usually too reactive for isolation and are potentially valuable for the fusion of additional rings by Diels-Alder reactions. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  7. Zirconacyclopentadiene-annulated polycyclic aromatic hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Kiel, Gavin R.; Ziegler, Micah S.; Tilley, T. Don [Department of Chemistry, University of California, Berkeley, CA (United States)

    2017-04-18

    Syntheses of large polycyclic aromatic hydrocarbons (PAHs) and graphene nanostructures demand methods that are capable of selectively and efficiently fusing large numbers of aromatic rings, yet such methods remain scarce. Herein, we report a new approach that is based on the quantitative intramolecular reductive cyclization of an oligo(diyne) with a low-valent zirconocene reagent, which gives a PAH with one or more annulated zirconacyclopentadienes (ZrPAHs). The efficiency of this process is demonstrated by a high-yielding fivefold intramolecular coupling to form a helical ZrPAH with 16 fused rings (from a precursor with no fused rings). Several other PAH topologies are also reported. Protodemetalation of the ZrPAHs allowed full characterization (including by X-ray crystallography) of PAHs containing one or more appended dienes with the ortho-quinodimethane (o-QDM) structure, which are usually too reactive for isolation and are potentially valuable for the fusion of additional rings by Diels-Alder reactions. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  8. Proficient synthesis of bioactive annulated pyrimidine derivatives: A review

    Directory of Open Access Journals (Sweden)

    Ajmal R. Bhat

    2017-11-01

    Full Text Available Syntheses of bioactive annulated pyrimidine derivatives are the most significant tasks in N-heterocyclic chemistry because these compounds have proved to be very attractive and useful for the design of new molecular frameworks of potential drugs with varying pharmacological activities. This review paper summarizes the one-pot multicomponent synthesis of annulated nitrogen- and oxygen-containing heterocycles, such as pyrano[2,3-d]pyrimidines, pyrido[2,3-d]pyrimidines and pyrido[2,3-d;5-6-d]dipyrimidines. The synthetic procedure is based on the chemistry of the domino Knoevenagel-Michael addition mechanism. Keywords: Pyrano[2,3-d]pyrimidines, Pyrido[2,3-d]pyrimidines, Pyrido[2,3-d;5-6-d]dipyrimidines, Barbituric acid/Thio-barbituric acid, Aromatic aldehydes, 6-aminouracil

  9. Columnar Self-Assembly of Electron-Deficient Dendronized Bay-Annulated Perylene Bisimides.

    Science.gov (United States)

    Gupta, Ravindra Kumar; Shankar Rao, Doddamane S; Prasad, S Krishna; Achalkumar, Ammathnadu S

    2018-03-07

    Three new heteroatom bay-annulated perylene bisimides (PBIs) have been synthesized by microwave-assisted synthesis in excellent yield. N-annulated and S-annulated perylene bisimides exhibited columnar hexagonal phase, whereas Se-annulated perylene bisimide exhibited low temperature columnar oblique phase in addition to the high temperature columnar hexagonal phase. The cup shaped bay-annulated PBIs pack into columns with enhanced intermolecular interactions. In comparison to PBI, these molecules exhibited lower melting and clearing temperature, with good solubility. A small red shift in the absorption was seen in the case of N-annulated PBI, whereas S- and Se-annulated PBIs exhibited blue-shifted absorption spectra. Bay-annulation increased the HOMO and LUMO levels of the N-annulated perylene bisimide, whereas a slight increase in the LUMO level and a decrease in the HOMO levels were observed in the case of S- and Se-annulated perylene bisimides, in comparison to the simple perylene bisimide. The band gaps of PBI and PBI-N were almost same, whereas an increase in the band gaps were observed in the case of S- and Se-annulated PBIs. The tendency to freeze in the ordered glassy columnar phase for PBI-N and PBI-S will help to overcome the charge traps due to crystallization, which are detrimental to one-dimensional charge carrier mobility. These solution processable electron deficient columnar semiconductors possessing good thermal stability may form an easily accessible promising class of n-type materials. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Regioselective annulation of nitrosopyridine with alkynes: straightforward synthesis of N-oxide-imidazopyridines.

    Science.gov (United States)

    Manna, Srimanta; Narayan, Rishikesh; Golz, Christopher; Strohmann, Carsten; Antonchick, Andrey P

    2015-04-11

    We have developed a novel method for the regioselective annulation of 2-nitrosopyridines with variably substituted alkynes under mild reaction conditions. This approach allows the annulation of alkynes with 2-nitrosopyridines under reagent- and catalyst-free reaction conditions. The developed method shows excellent functional group tolerance and provides easy access to N-oxide-imidazo[1,2-a]pyridines.

  11. N -annulated perylene-based push-pull-type sensitizers

    KAUST Repository

    Qi, Qingbiao; Wang, Xingzhu; Fan, Li; Zheng, Bin; Zeng, Wangdong; Luo, Jie; Huang, Kuo-Wei; Wang, Qing; Wu, Jishan

    2015-01-01

    Alkoxy-wrapped N-annulated perylene (NP) was synthesized and used as a rigid and coplanar π-linker for three push-pull type metal-free sensitizers QB1-QB3. Their optical and electrochemical properties were tuned by varying the structure of acceptor. These new dyes were applied in Co(II)/(III) based dye-sensitized solar cells, and power conversion efficiency up to 6.95% was achieved, indicating that NP could be used as a new building block for the design of high-performance sensitizers in the future.

  12. N -annulated perylene-based push-pull-type sensitizers

    KAUST Repository

    Qi, Qingbiao

    2015-02-06

    Alkoxy-wrapped N-annulated perylene (NP) was synthesized and used as a rigid and coplanar π-linker for three push-pull type metal-free sensitizers QB1-QB3. Their optical and electrochemical properties were tuned by varying the structure of acceptor. These new dyes were applied in Co(II)/(III) based dye-sensitized solar cells, and power conversion efficiency up to 6.95% was achieved, indicating that NP could be used as a new building block for the design of high-performance sensitizers in the future.

  13. Action for declaration of annulment of reactor construction permit dismissed

    International Nuclear Information System (INIS)

    Anon.

    1982-01-01

    The Higher Administrative Court of Rheinland Pfalz has confirmed two decisions by the Koblenz Administrative Court dismissing an actions to declare the annulment of the partial construction permit issued for the Muelheim-Kaerlich reactor. Appeal was not admitted. The plaintiffs, who are under age and were represented by their father, are permanently resident in Schleswig-Holstein, at about 470 km from the site and have a further residence in Mainz, about 60 km away from the site. They plead to have a legitimate interest in the declaration of nullity on the grounds of the uncertainty created in legal matters by the delivery of the permit and its being unconstitutional as well as for ideological and religious reasons. The ruling deals also with the importance of the distance from the site of a nuclear reactor, which is considered to be such as to exclude the 'necessary spatial relation'. (orig./HP) [de

  14. Radical-mediated annulation reactions. A versatile strategy for the preparation of a series of carbocycles.

    Science.gov (United States)

    Sibi, M P; Chen, J; Rheault, T R

    2001-11-15

    [reaction--see text] A series of novel 6-endo [4 + 2] and 7-endo [5 + 2] radical-mediated annulation reactions are described. These annulation sequences involve an intermolecular radical addition followed by intramolecular trapping with an allyltin moiety incorporated into the radical precursor fragment. This methodology allows for access to functionalized 6- and 7-membered carbocycles as well as bicyclic compounds with good to excellent levels of stereocontrol.

  15. N-annulated perylene fused porphyrins with enhanced near-IR absorption and emission

    KAUST Repository

    Jiao, Chongjun

    2010-09-17

    N-Annulated perylene fused porphyrins 1 and 2 were synthesized by oxidative dehydrogenation using a Sc(OTf)3/DDQ system. These newly synthesized hybrid molecules are highly soluble in organic solvents and exhibit remarkably intense near-IR absorption, as well as detectable photoluminescence quantum yields, all of which are comparable to or even exceed those of either meso-β doubly linked porphyrin dimer/trimer or bis/tri-N-annulated rylenes. © 2010 American Chemical Society.

  16. Mechanism of Intramolecular Rhodium- and Palladium-Catalyzed Alkene Alkoxyfunctionalizations

    KAUST Repository

    Vummaleti, Sai V. C.; Alghamdi, Miasser; Poater, Albert; Falivene, Laura; Scaranto, Jessica; Beetstra, Dirk J.; Morton, Jason G.; Cavallo, Luigi

    2015-01-01

    Density functional theory calculations have been used to investigate the reaction mechanism for the [Rh]-catalyzed intramolecular alkoxyacylation ([Rh] = [RhI(dppp)+] (dppp, 1,3-bis(diphenylphosphino)propane) and [Pd]/BPh3 dual catalytic system assisted intramolecular alkoxycyanation ([Pd] = Pd-Xantphos) using acylated and cyanated 2-allylphenol derivatives as substrates, respectively. Our results substantially confirm the proposed mechanism for both [Rh]- and [Pd]/ BPh3-mediated alkoxyfunctionalizations, offering a detailed geometrical and energetical understanding of all the elementary steps. Furthermore, for the [Rh]-mediated alkoxyacylation, our observations support the hypothesis that the quinoline group of the substrate is crucial to stabilize the acyl metal complex and prevent further decarbonylation. For [Pd]/BPh3-catalyzed alkoxycyanation, our findings clarify how the Lewis acid BPh3 cocatalyst accelerates the only slow step of the reaction, corresponding to the oxidative addition of the cyanate O-CN bond to the Pd center. © 2015 American Chemical Society.

  17. Mechanism of Intramolecular Rhodium- and Palladium-Catalyzed Alkene Alkoxyfunctionalizations

    KAUST Repository

    Vummaleti, Sai V. C.

    2015-11-13

    Density functional theory calculations have been used to investigate the reaction mechanism for the [Rh]-catalyzed intramolecular alkoxyacylation ([Rh] = [RhI(dppp)+] (dppp, 1,3-bis(diphenylphosphino)propane) and [Pd]/BPh3 dual catalytic system assisted intramolecular alkoxycyanation ([Pd] = Pd-Xantphos) using acylated and cyanated 2-allylphenol derivatives as substrates, respectively. Our results substantially confirm the proposed mechanism for both [Rh]- and [Pd]/ BPh3-mediated alkoxyfunctionalizations, offering a detailed geometrical and energetical understanding of all the elementary steps. Furthermore, for the [Rh]-mediated alkoxyacylation, our observations support the hypothesis that the quinoline group of the substrate is crucial to stabilize the acyl metal complex and prevent further decarbonylation. For [Pd]/BPh3-catalyzed alkoxycyanation, our findings clarify how the Lewis acid BPh3 cocatalyst accelerates the only slow step of the reaction, corresponding to the oxidative addition of the cyanate O-CN bond to the Pd center. © 2015 American Chemical Society.

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

    NARCIS (Netherlands)

    Gümrükçü, Y.

    2014-01-01

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

  19. Tailoring Colors by O Annulation of Polycyclic Aromatic Hydrocarbons.

    Science.gov (United States)

    Miletić, Tanja; Fermi, Andrea; Orfanos, Ioannis; Avramopoulos, Aggelos; De Leo, Federica; Demitri, Nicola; Bergamini, Giacomo; Ceroni, Paola; Papadopoulos, Manthos G; Couris, Stelios; Bonifazi, Davide

    2017-02-16

    The synthesis of O-doped polyaromatic hydro- carbons in which two polycyclic aromatic hydrocarbon sub units are bridged through one or two O atoms has been achieved. This includes high-yield ring-closure key steps that, depending on the reaction conditions, result in the formation of furanyl or pyranopyranyl linkages through intramolecular C-O bond formation. Comprehensive photophysical measurements in solution showed that these compounds have exceptionally high emission yields and tunable absorption properties throughout the UV/Vis spectral region. Electrochemical investigations showed that in all cases O annulation increases the electron-donor capabilities by raising the HOMO energy level, whereas the LUMO energy level is less affected. Moreover, third-order nonlinear optical (NLO) measurements on solutions or thin films containing the dyes showed very good values of the second hyperpolarizability. Importantly, poly(methyl methacrylate) films containing the pyranopyranyl derivatives exhibited weak linear absorption and NLO absorption compared to the nonlinearity and NLO refraction, respectively, and thus revealed them to be exceptional organic materials for photonic devices. © 2016 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

  20. Nitrile-assisted oxidation over oxidative-annulation: Pd-catalyzed α,β-dehydrogenation of α-cinnamyl β-keto nitriles.

    Science.gov (United States)

    Nallagonda, Rajender; Reddy, Reddy Rajasekhar; Ghorai, Prasanta

    2017-09-13

    A palladium-catalyzed oxidation reaction is disclosed where the nitrile functionality on the substrate simply changes the course of the reaction. Our previous finding showed that using the Pd(ii)-catalyst in the presence of benzoquinone as an oxidant, 2-cinnamyl-1,3-dicarbonyls provides functionalized furans via oxidative cyclization. When a nitrile group is replaced with one of the carbonyl functionalities of the same substrate, the oxidative cyclization was completely suppressed; instead, the oxidation at the α,β-position occurred to provide α,β,γ,δ-diene containing β-keto nitriles.

  1. Redox-Neutral Rhodium-Catalyzed [4+1] Annulation through Formal Dehydrogenative Vinylidene Insertion.

    Science.gov (United States)

    Liu, Huan; Song, Shengjin; Wang, Cheng-Qiang; Feng, Chao; Loh, Teck-Peng

    2017-01-10

    A synthetic protocol for the expedient construction of 5-methylene-1H-pyrrol-2(5H)-one derivatives through rhodium-catalyzed [4+1] annulation with gem-difluoroacrylate as the C 1 component was reported. By taking advantage of the twofold C-F bond cleavage occurring during the annulation, this reaction not only allows the synthesis of these heterocyclic compounds under overall oxidant-free conditions but also renders the transformation stereospecific. The very mild reaction conditions employed ensure compatibility with a wide variety of synthetically useful functional groups. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Annulation of β-naphthols and 4-hydroxycoumarins with vinylsulfonium salts: synthesis of dihydrofuran derivatives.

    Science.gov (United States)

    Chen, Zi-Cong; Tong, Lang; Du, Zhi-Bo; Mao, Zhi-Feng; Zhang, Xue-Jing; Zou, Yong; Yan, Ming

    2018-04-18

    A new synthetic approach to dihydrofuran derivatives via the annulation reaction of β-naphthols and 4-hydroxycoumarins with vinylsulfonium salts has been developed. A variety of dihydrofuran derivatives were prepared in moderate to good yields under mild conditions. The products could be readily transformed to the corresponding furans via the dehydrogenation with DDQ.

  3. Synthesis of Quinolines through Three-Component Cascade Annulation of Aryl Diazonium Salts, Nitriles, and Alkynes.

    Science.gov (United States)

    Wang, Hao; Xu, Qian; Shen, Sheng; Yu, Shouyun

    2017-01-06

    An efficient and rapid synthesis of multiply substituted quinolines is described. This method is enabled by a three-component cascade annulation of readily available aryl diazonium salts, nitriles, and alkynes. This reaction is catalyst- and additive-free. Various aryl diazonium salts, nitriles, and alkynes can participate in this transformation, and the yields are up to 83%.

  4. N-annulated perylene fused porphyrins with enhanced near-IR absorption and emission

    KAUST Repository

    Jiao, Chongjun; Huang, Kuo-Wei; Guan, Zhenping; Xu, Qinghua; Wu, Jishan

    2010-01-01

    -IR absorption, as well as detectable photoluminescence quantum yields, all of which are comparable to or even exceed those of either meso-β doubly linked porphyrin dimer/trimer or bis/tri-N-annulated rylenes. © 2010 American Chemical Society.

  5. Synthesis of tetrahydrokhusitone. Annulation of the cyclohexane ring by free radical and carbanionic sequence of reactions

    Directory of Open Access Journals (Sweden)

    ZIVORAD CEKOVIC

    2003-05-01

    Full Text Available The synthesis of norcadinane sesquiterpene tetrahydrokhusitone 1 has been achieved by a new method for annulation of cyclohexane ring involving a sequence of free radical d-alkylation of the non-activated carbon atom and intramolecular carbanionic alkylation. (–-Menthol was used as the starting compound.

  6. Enantioselective [3+3] atroposelective annulation catalyzed by N-heterocyclic carbenes

    KAUST Repository

    Zhao, Changgui; Guo, Donghui; Munkerup, Kristin; Huang, Kuo-Wei; Li, Fangyi; Wang, Jian

    2018-01-01

    on the transition-metal-catalyzed transformations. Here, we report the enantioselective NHC-catalyzed (NHC: N-heterocyclic carbenes) atroposelective annulation of cyclic 1,3-diones with ynals. In the presence of NHC precatalyst, base, Lewis acid and oxidant, a

  7. Combining silver- and organocatalysis: an enantioselective sequential catalytic approach towards pyrano-annulated pyrazoles.

    Science.gov (United States)

    Hack, Daniel; Chauhan, Pankaj; Deckers, Kristina; Mizutani, Yusuke; Raabe, Gerhard; Enders, Dieter

    2015-02-11

    A one-pot asymmetric Michael addition/hydroalkoxylation sequence, catalyzed by a sequential catalytic system consisting of a squaramide and a silver salt, provides a new series of chiral pyrano-annulated pyrazole derivatives in excellent yields (up to 95%) and high enantioselectivities (up to 97% ee).

  8. Rhodium Catalyzed Annulation of N-Benzoylsulfonamide with Isocyanide via C-H Activation

    Science.gov (United States)

    Zhu, Chen; Xie, Weiqing; Falck, John R.

    2012-01-01

    Isocyanide insertion: the first rhodium-catalyzed annulation of N-benzoylsulfonamide incorporating with isocyanide via C-H activation is described. The transformation is broadly compatible with N-benzoylsulfonamides bearing various electron-properties as well as isocyanides. From practical point of view, this methodology provides the most straightforward approach to a series of 3-(imino)isoindolinones. PMID:21972033

  9. Rh-Catalyzed Annulations of N-Methoxybenzamides and Ketenimines: Sterically and Electronically Controlled Synthesis of Isoquinolinones and Isoindolinones.

    Science.gov (United States)

    Zhou, Xiaorong; Zhang, Zhiyin; Zhao, Hongyang; Lu, Ping; Wang, Yanguang

    2017-04-07

    Rhodium-catalyzed C-H activation/annulation reactions of ketenimines with N-methoxybenzamides are reported. The outcome of reactions is dependent on the structure of ketenimines. The β-alkyl-substituted ketenimines furnish 3-iminoisoquinolin-1(2H)-ones in a formal [4 + 2] annulation manner, while the β-ester substituted ketenimines afford 3-aminoisoindolin-1-ones in a formal [4 + 1] annulation manner. The synthesized [4 + 2] products undergo an intramolecular Cu-catalyzed C-N coupling to be converted to benzo[4,5]imidazo[1,2-b]isoquinolin-11-ones, which can be directly prepared from ketenimines and N-methoxybenzamides by a one-pot Rh-catalyzed annulation/Cu-catalyzed C-N coupling sequence.

  10. [Evaluation of Articles 33 and 59, of the Code of Deontology of Doctors in Catalonia (2005), judicially annulled].

    Science.gov (United States)

    Collazo Chao, Eliseo

    2009-01-01

    At the end of the year 2004, the Autonomous Conseil of the Medical School in Catalonia (Spain) approved its Deontology Code. The articles 33 and 59 were then judicially resorted by more than one hundred doctors in Catalonia; nowadays those articles themselves have been annulled by judicial sentence. This research aims to accomplish a valuation ethical and deontological of the annulled articles, according to the statutes.

  11. N-Annulated Perylene as a Donor in Cyclopentadithiophene Based Sensitizers: The Effect of Linking Mode

    KAUST Repository

    Luo, Jie; Wang, Xingzhu; Fan, Li; Li, Gongqiang; Qi, Qingbiao; Huang, Kuo-Wei; Tam, Teck Lip Dexter; Zhang, Jie; Wang, Qing; Wu, Jishan

    2015-01-01

    Two types of cyclopentadithiophene dyes with different linking modes with an N-annulated perylene (NP) donor were designed and synthesized. These new dyes were applied in Co(II)/(III) based dye-sensitized solar cells and an efficiency up to 7.8% could be obtained for peri-NP linked CPD-1. The effect of the linking mode on the material properties and device performance was discussed.

  12. N-Annulated Perylene as a Donor in Cyclopentadithiophene Based Sensitizers: The Effect of Linking Mode

    KAUST Repository

    Luo, Jie

    2015-11-24

    Two types of cyclopentadithiophene dyes with different linking modes with an N-annulated perylene (NP) donor were designed and synthesized. These new dyes were applied in Co(II)/(III) based dye-sensitized solar cells and an efficiency up to 7.8% could be obtained for peri-NP linked CPD-1. The effect of the linking mode on the material properties and device performance was discussed.

  13. Divergent Reactivity of Rhodium(I) Carbenes Derived from Indole Annulations.

    Science.gov (United States)

    Li, Xiaoxun; Li, Hui; Song, Wangze; Tseng, Po-Sen; Liu, Lingyan; Guzei, Ilia A; Tang, Weiping

    2015-10-26

    Rhodium(I) carbenes were generated from propargylic alcohol derivatives as the result of a dehydrative indole annulation. Depending on the choice of the electron-withdrawing group on the aniline nitrogen nucleophile, either a cyclopropanation product or dimerization product was obtained chemoselectively. Intramolecular hydroamidation occurred for the same type of propargylic alcohol derivatives when other transition-metal catalysts were employed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. In vivo photoacoustic tumor tomography using a quinoline-annulated porphyrin as NIR molecular contrast agent.

    Science.gov (United States)

    Luciano, Michael; Erfanzadeh, Mohsen; Zhou, Feifei; Zhu, Hua; Bornhütter, Tobias; Röder, Beate; Zhu, Quing; Brückner, Christian

    2017-01-25

    The synthesis and photophysical properties of a tetra-PEG-modified and freely water-soluble quinoline-annulated porphyrin are described. We previously demonstrated the ability of quinoline-annulated porphyrins to act as an in vitro NIR photoacoustic imaging (PAI) contrast agent. The solubility of the quinoline-annulated porphyrin derivative in serum now allowed the assessment of the efficacy of the PEGylated derivative as an in vivo NIR contrast agent for the PAI of an implanted tumor in a mouse model. A multi-fold contrast enhancement when compared to the benchmark dye ICG could be shown, a finding that could be traced to its photophysical properties (short triplet lifetimes, low fluorescence and singlet oxygen sensitization quantum yields). A NIR excitation wavelength of 790 nm could be used, fully taking advantage of the optical window of tissue. Rapid renal clearance of the dye was observed. Its straight-forward synthesis, optical properties with the possibility for further optical fine-tuning, nontoxicity, favorable elimination rates, and contrast enhancement make this a promising PAI contrast agent. The ability to conjugate the PAI chromophore with a fluorescent tag using a facile and general conjugation strategy was also demonstrated.

  15. Isomeric N-Annulated Perylene Diimide Dimers for Organic Solar Cells.

    Science.gov (United States)

    Ma, Zetong; Fu, Huiting; Meng, Dong; Jiang, Wei; Sun, Yanming; Wang, Zhaohui

    2018-04-16

    Two isomeric N-annulated perylene diimide dimers, namely, p-BDNP and m-BDNP were designed and synthesized via geometric tuning. The distinct molecular geometry and packing arrangements of isomers with almost identical optical and electrochemical properties rendered us an in-depth understanding of the molecular structure-aggregation state-photovoltaic performance relationship. Blended with the commercially available donor PCE-10, p-BDNP and m-BDNP showed distinct differences in photovoltaic performance with power conversion efficiencies (PCEs) of 5.01 % and 4.15 %, respectively. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Enantioselective Access to Spirocyclic Sultams by Chiral Cp(x) -Rhodium(III)-Catalyzed Annulations.

    Science.gov (United States)

    Pham, Manh V; Cramer, Nicolai

    2016-02-12

    Chiral spirocyclic sultams are a valuable compound class in organic and medicinal chemistry. A rapid entry to this structural motif involves a [3+2] annulation of an N-sulfonyl ketimine and an alkyne. Although the directing-group properties of the imino group for C-H activation have been exploited, the developments of related asymmetric variants have remained very challenging. The use of rhodium(III) complexes equipped with a suitable atropchiral cyclopentadienyl ligand, in conjunction with a carboxylic acid additive, enables an enantioselective and high yielding access to such spirocyclic sultams. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Lewis acid catalyzed [3 + 2] annulation of ketenimines with donor-acceptor cyclopropanes: an approach to 2-alkylidenepyrrolidine derivatives.

    Science.gov (United States)

    Alajarin, Mateo; Egea, Adrian; Orenes, Raul-Angel; Vidal, Angel

    2016-11-02

    The [3 + 2] annulation reaction of C,C,N-trisubstituted ketenimines with donor-acceptor cyclopropanes bearing aryl, styryl and vinyl substituents at the C2 position, triggered by the Lewis acid Sc(OTf) 3 , supplies highly substituted pyrrolidines. Activated cyclopropanes fused to naphthalene and [1]benzopyrane nuclei are also suitable substrates in similar transformations, yielding partially saturated benz[g]indoles and [1]benzopyran[4,3-b]pyrroles. An intramolecular version of this ketenimine/cyclopropane [3 + 2] annulation has also been developed leading to the pyrrolo[2,1-a]isoindole framework.

  18. Electrooxidative Ruthenium-Catalyzed C-H/O-H Annulation by Weak O-Coordination.

    Science.gov (United States)

    Qiu, Youai; Tian, Cong; Massignan, Leonardo; Rogge, Torben; Ackermann, Lutz

    2018-05-14

    Electrocatalysis has been identified as a powerful strategy for organometallic catalysis, and yet electrocatalytic C-H activation is restricted to strongly N-coordinating directing groups. The first example of electrocatalytic C-H activation by weak O-coordination is presented, in which a versatile ruthenium(II) carboxylate catalyst enables electrooxidative C-H/O-H functionalization for alkyne annulations in the absence of metal oxidants; thereby exploiting sustainable electricity as the sole oxidant. Mechanistic insights provide strong support for a facile organometallic C-H ruthenation and an effective electrochemical reoxidation of the key ruthenium(0) intermediate. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Enantioselective [3+3] atroposelective annulation catalyzed by N-heterocyclic carbenes

    KAUST Repository

    Zhao, Changgui

    2018-02-05

    Axially chiral molecules are among the most valuable substrates in organic synthesis. They are typically used as chiral ligands or catalysts in asymmetric reactions. Recent progress for the construction of these chiral molecules is mainly focused on the transition-metal-catalyzed transformations. Here, we report the enantioselective NHC-catalyzed (NHC: N-heterocyclic carbenes) atroposelective annulation of cyclic 1,3-diones with ynals. In the presence of NHC precatalyst, base, Lewis acid and oxidant, a catalytic C–C bond formation occurs, providing axially chiral α-pyrone−aryls in moderate to good yields and with high enantioselectivities. Control experiments indicated that alkynyl acyl azoliums, acting as active intermediates, are employed to atroposelectively assemble chiral biaryls and such a methodology may be creatively applied to other useful NHC-catalyzed asymmetric transformations.

  20. Annulate lamellae in phloem cells of virus-infected Sonchus plants.

    Science.gov (United States)

    Steinkamp, M P; Hoefert, L L

    1977-07-01

    The occurrence of annulate lamellae (AL) in differentiating phloem of Sonchus oleraceus (Compositae) singly infected with sowthistle yellow vein virus (SYVV) and doubly infected with a combination of SYVV and beet yellow stunt virus is documented by electron microscopy. Cell types in which AL were found were immature sieve elements and phloem parenchyma cells. AL were found only in cells that also contained SYVV particles although a direct association between the virus and AL was not apparent. The substructure of the AL and the relationships between the AL and the nuclear envelope and endoplasmic reticulum are similar to those reported in other descriptions of this organelle in the literature. This report appears to be the first one concerning the association of AL with a plant virus disease.

  1. Synthesis of isochromene-type scaffolds via single-flask Diels-Alder-[4 + 2]-annulation sequence of a silyl-substituted diene with menadione.

    Science.gov (United States)

    Lee, Jihoon; Panek, James S

    2014-06-20

    A sequential Diels-Alder reaction/silicon-directed [4 + 2]-annulation was developed to assemble hydroisochromene-type ring systems from menadione 2. In the first step, a Diels-Alder of the 1-silyl-substituted butadiene 1 with 2 furnished an intermediate cyclic allylsilane. Subsequently, TMSOTf promoted a [4 + 2]-annulation through trapping of an oxonium, generated by condensation between an aldehyde and the TBS protected alcohol resulted in the formation of a cis-fused hydroisochromene 13.

  2. [1+1+3] Annulation of Diazoenals and Vinyl Azides: Direct Synthesis of Functionalized 1-Pyrrolines through Olefination.

    Science.gov (United States)

    Kanchupalli, Vinaykumar; Katukojvala, Sreenivas

    2018-05-04

    A dirhodium carboxylate catalyzed [1+1+3] annulation reaction of diazoenals and vinyl azides that gives synthetically important enal-functionalized 1-pyrroline derivatives was developed. The reaction involves a novel rhodium-catalyzed olefination of diazoenals with vinyl azides via electrophilic enal carbenoids, resulting in a new class of enal acrylates. The annulation reaction was used for the direct synthesis of valuable deuterated 1-pyrrolines. Structural diversification of the enal-functionalized 1-pyrrolines resulted in the biologically important pyrrolidine-fused oxaziridine, amino acid derivatives, and a 6-azabicyclo[3.2.1]octane motif present in polycyclic alkaloids. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Cobalt-mediated [3 + 2]-annulation reaction of alkenes with alpha,beta-unsaturated ketones and imines.

    Science.gov (United States)

    Schomaker, Jennifer M; Toste, F Dean; Bergman, Robert G

    2009-08-20

    The utility of cobalt dinitrosyl complexes for the [3 + 2] annulation of alkenes with unsaturated enones and ketimines has been demonstrated. Reaction of a series of cobalt dinitrosyl/alkene adducts with conjugate acceptors in the presence of Sc(OTf)(3)/LHMDS formed two new C-C bonds at the carbons alpha to the nitrosyl groups of the substrate, leading to unusual tri- and tetracycles. Retrocycloaddition of these products in the presence of norbornadiene yielded functionalized tetrasubstituted bicyclic olefins.

  4. Formation of benzo[f]-1-indanone frameworks by regulable intramolecular annulations of gem-dialkylthio trienynes.

    Science.gov (United States)

    Fang, Zhongxue; Liu, Ying; Barry, Badru-Deen; Liao, Peiqiu; Bi, Xihe

    2015-02-20

    An atom-economic route to benzo[f]-1-indanone frameworks has been developed starting from the readily available gem-dialkylthio trienynes by intramolecular annulations. The chemoselectivity of the intramolecular cyclizations can be regulated by both the base and the type of gas atmosphere used in the reaction, thus allowing the divergent synthesis of the corresponding functionalized benzo[f]-1-indanones in good to excellent yields.

  5. Bay-annulated indigo (BAI) as an excellent electron accepting building block for high performance organic semiconductors

    Science.gov (United States)

    Liu, Yi; He, Bo; Pun, Andrew

    2015-11-24

    A novel electron acceptor based on bay-annulated indigo (BAI) was synthesized and used for the preparation of a series of high performance donor-acceptor small molecules and polymers. The resulting materials possess low-lying LUMO energy level and small HOMO-LUMO gaps, while their films exhibited high crystallinity upon thermal treatment, commensurate with high field effect mobilities and ambipolar transfer characteristics.

  6. I. The synthesis and characterization of annulated uranocenes. II. The variable temperature 1H NMR of uranocenes

    International Nuclear Information System (INIS)

    Luke, W.D.

    1980-01-01

    A general synthetic route to alkyl annulated cyclooctatetraene dianions and the corresponding annulated uranocenes has been developed. Dideprotonation of bicyclooctatrienes, resulting from reaction of cyclooctatetraene dianion with l,n-dialkylbromides or methanesulfonates, affords alkyl annulated cyclooctatetraene dianions in moderate yields. Dicyclopenteno-, bisdimethylcyclopenteno- and dicyclohexenouranocene were prepared from the corresponding cyclooctatetraene dianions and UCl 4 . The structures of dicyclobuteno- and dicyclopentenouranocene were elucidated by single crystal X-ray diffraction, and the effects of annulation on the uranocene skeleton are discussed. Attempted synthesis of benzocyclooctatetraene and a benzannulated uranocene is reported. The variable temperature 1 H NMR spectrum of uranocene has been reinvestigated from -100 to 100 0 C. The isotropic shift was found to be linear in T -1 with an extrapolated intercept of 0 at T -1 = 0. Variable temperature 1 H NMR spectra, from -80 to 70 0 C, of 17 substituted uranocenes are reported. The energy barrier to ring rotation in 1,1', 4,4'-tetra-t-butyl-uranocene was determined to be 8.24 +- 0.5 kcal/mole while the barrier in the corresponding 1,1', 3,3'-tetra-t-butylferrocene was determined to be 13.1 kcal/mole. Alkyl substitution is shown to have little effect on the electronic and magnetic properties of the uranocene skeleton, and thus alkyl substituted uranocenes are treated as having effective axial symmetry in analysis of the observed isotropic shifts. Using diannulated uranocenes as model systems an analysis of the contact and pseudocontact components of the observed isotropic shifts in uranocene and alkyl substituted uranocenes is presented

  7. Total synthesis of complestatin: development of a Pd(0)-mediated indole annulation for macrocyclization.

    Science.gov (United States)

    Shimamura, Hiroyuki; Breazzano, Steven P; Garfunkle, Joie; Kimball, F Scott; Trzupek, John D; Boger, Dale L

    2010-06-09

    Full details of the initial development and continued examination of a powerful intramolecular palladium(0)-mediated indole annulation for macrocyclization closure of the strained 16-membered biaryl ring system found in complestatin (1, chloropeptin II) and the definition of factors impacting its intrinsic atropodiastereoselectivity are described. Its examination and use in an alternative, second-generation total synthesis of complestatin are detailed in which the order of the macrocyclization reactions was reversed from our first-generation total synthesis. In this approach and with the ABCD biaryl ether ring system in place, the key Larock cyclization was conducted with substrate 36 (containing four phenols, five secondary amides, one carbamate, and four labile aryl chlorides) and provided the product 37 (56%) exclusively as a single atropisomer (>20:1, detection limits) possessing the natural (R)-configuration. In this instance, the complexity of the substrate and the reverse macrocyclization order did not diminish the atropodiastereoselectivity; rather, it provided an improvement over the 4:1 selectivity that was observed with the analogous substrate used to provide the isolated DEF ring system in our first-generation approach. Just as significant, the atroposelectivity represents a complete reversal of the diasteroselectivity observed with analogous macrocyclizations conducted using a Suzuki biaryl coupling.

  8. Thermally Induced Denitrogenative Annulation for the Synthesis of Dihydroquinolinimines and Chroman-4-imines.

    Science.gov (United States)

    Chou, Chih-Hung; Chen, Ying-Yu; Rajagopal, Basker; Tu, Hsiu-Chung; Chen, Kuan-Lin; Wang, Sheng-Fu; Liang, Chien-Fu; Tyan, Yu-Chang; Lin, Po-Chiao

    2016-03-04

    A rapid growth in synthetic methods for the preparation of diverse organic molecules using N-sulfonyl-1,2,3-triazoles is of great interest in organic synthesis. Transition metals are generally used to activate the α-imino diazo intermediates. Metal-free methods have not been studied in detail, but can be a good complement to transition metal catalysis in the mild reaction conditions. We herein report a novel method for the preparation of 2,3-dihydroquinolin-4-imine and chroman-4-imine analogs from their corresponding N-sulfonyl-1,2,3-triazoles in the absence of metal catalysts. To achieve intramolecular annulation, the introduction of an electron-donating group is required at the meta position of N-sulfonyl-1,2,3-triazole methyl anilines. The inclusion of tailored substituents on the aniline moieties and nitrogen atoms enhances the nucleophilicity of the phenyl π-electrons, thus allowing them to undergo a Friedel-Crafts-type reaction with the highly electrophilic ketenimines. This metal-free method was carefully optimized to generate a variety of dihydroquinolin-4-imines and chroman-4-imines in moderate-to-good yields. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. From pirazoloquinolines to annulated azulene dyes: UV-VIS spectroscopy and quantum chemical study

    International Nuclear Information System (INIS)

    Gasiorski, P.; Danel, K.S.; Matusiewicz, M.; Uchacz, T.; Kityk, A.V.

    2010-01-01

    Paper reports UV-Vis absorption and photoluminescence spectra of 6-R derivatives (R=CH 3 , O-CH 3 , C(C 6 H 5 ) 3 , C 6 H 5 -N-C 10 H 7 ) of 4-(2-chlorophenyl)-1,3-diphenyl-1H-pyrazolo[3,4-b]quinoline, belonging to pyrazoloquinoline (PQ) family, likewise its regioisomeric products 10-R derivatives of 6-phenyl-6H-5,6,7-triazadibenzo[f,h]naphtho[3,2,1-cd]azulene representing cyclized seven-membered annulated azulene (AA) dyes. Cyclization of PQs into AAs is accompanied by a significant red shift of the first optical absorption band. This finding agrees with the results of quantum-chemical calculations performed by means of the semiempirical method PM3. As the solvent polarity rises all the dyes exhibit a blue shift of the first absorption band and a red shift of the fluorescence band. Such opposite trends in solvatochromic behavior have been reproduced within the semiempirical calculations in combination with the Lippert-Mataga dielectric polarization model. Depending on solvent polarity AA dyes emit light in the green, green-yellow or orange range of the visible spectrum what may be of interest for potential luminescent or electroluminescent applications.

  10. Facile palladium catalyzed Suzuki-Miyaura coupling in air and water at ambient temperature

    KAUST Repository

    Marziale, Alexander N.; Faul, Stefan Holger; Reiner, Thomas; Schneider, Sven; Eppinger, Jö rg

    2010-01-01

    A new palladacyclic catalyst yields high activities in aqueous Suzuki-Miyaura coupling at room temperature. Using an optimized protocol, a broad range of products can be isolated in good to excellent yields and high purity by simple filtration. © 2010 The Royal Society of Chemistry.

  11. Toward Green Acylation of (Heteroarenes: Palladium-Catalyzed Carbonylation of Olefins to Ketones

    Directory of Open Access Journals (Sweden)

    Jie Liu

    2017-11-01

    Full Text Available Green Friedel–Crafts acylation reactions belong to the most desired transformations in organic chemistry. The resulting ketones constitute important intermediates, building blocks, and functional molecules in organic synthesis as well as for the chemical industry. Over the past 60 years, advances in this topic have focused on how to make this reaction more economically and environmentally friendly by using green acylating conditions, such as stoichiometric acylations and catalytic homogeneous and heterogeneous acylations. However, currently well-established methodologies for their synthesis either produce significant amounts of waste or proceed under harsh conditions, limiting applications. Here, we present a new protocol for the straightforward and selective introduction of acyl groups into (hetero­arenes without directing groups by using available olefins with inexpensive CO. In the presence of commercial palladium catalysts, inter- and intramolecular carbonylative C–H functionalizations take place with good regio- and chemoselectivity. Compared to classical Friedel–Crafts chemistry, this novel methodology proceeds under mild reaction conditions. The general applicability of this methodology is demonstrated by the direct carbonylation of industrial feedstocks (ethylene and diisobutene as well as of natural products (eugenol and safrole. Furthermore, synthetic applications to drug molecules are showcased.

  12. Palladium-Catalyzed Suzuki–Miyaura Cross-Coupling in Continuous Flow

    Directory of Open Access Journals (Sweden)

    Christophe Len

    2017-05-01

    Full Text Available Carbon–carbon cross-coupling reactions are among the most important processes in organic chemistry and Suzuki–Miyaura reactions are the most widely used protocols. For a decade, green chemistry and particularly catalysis and continuous flow, have shown immense potential in achieving the goals of “greener synthesis”. To date, it seems difficult to conceive the chemistry of the 21st century without the industrialization of continuous flow process in the area of pharmaceuticals, drugs, agrochemicals, polymers, etc. A large variety of palladium Suzuki–Miyaura cross-coupling reactions have been developed using a continuous flow sequence for preparing the desired biaryl derivatives. Our objective is to focus this review on the continuous flow Suzuki–Miyaura cross-coupling using homogeneous and heterogeneous catalysts.

  13. Ligand-free, palladium-catalyzed dihydrogen generation from TMDS: dehalogenation of aryl halides on water.

    Science.gov (United States)

    Bhattacharjya, Anish; Klumphu, Piyatida; Lipshutz, Bruce H

    2015-03-06

    A mild and environmentally attractive dehalogenation of functionalized aryl halides has been developed using nanoparticles formed from PdCl2 in the presence of tetramethyldisiloxane (TMDS) on water. The active catalyst and reaction medium can be recycled. This method can also be applied to cascade reactions in a one-pot sequence.

  14. Applications of Palladium-Catalyzed C-N Cross-Coupling Reactions.

    Science.gov (United States)

    Ruiz-Castillo, Paula; Buchwald, Stephen L

    2016-10-12

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

  15. The mechanism of the phosphine-free palladium-catalyzed hydroarylation of alkynes

    DEFF Research Database (Denmark)

    Ahlquist, Mårten Sten Gösta; Fabrizi, G.; Cacchi, S.

    2006-01-01

    The mechanism of the Pd-catalyzed hydroarylation and hydrovinylation reaction of alkynes has been studied by a combination of experimental and theoretical methods (B3LYP), with an emphasis on the phosphine-free version. The regioselectivity of the hydroarylation and hydrovinylation shows unexpected...

  16. Alkanes from Bioderived Furans by using Metal Triflates and Palladium-Catalyzed Hydrodeoxygenation of Cyclic Ethers.

    Science.gov (United States)

    Song, Hai-Jie; Deng, Jin; Cui, Min-Shu; Li, Xing-Long; Liu, Xin-Xin; Zhu, Rui; Wu, Wei-Peng; Fu, Yao

    2015-12-21

    Using a metal triflate and Pd/C as catalysts, alkanes were prepared from bioderived furans in a one-pot hydrodeoxygenation (HDO) process. During the reaction, the metal triflate plays a crucial role in the ring-opening HDO of furan compounds. The entire reaction process has goes through two major phases: at low temperatures, saturation of the exocyclic double bond and furan ring are catalyzed by Pd/C; at high temperatures, the HDO of saturated furan compounds is catalyzed by the metal triflate. The reaction mechanism was verified by analyzing the changes of the intermediates during the reaction. In addition, different metal triflates, solvents, and catalyst recycling were also investigated. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Palladium-Catalyzed Telomerization of Butadiene with Polyols: From Mono to Polysaccharides

    Science.gov (United States)

    Bouquillon, Sandrine; Muzart, Jacques; Pinel, Catherine; Rataboul, Franck

    The telomerization of butadiene with alcohols is an elegant way to synthesize ethers with minimal environmental impact since this reaction is 100% atom efficient. Besides telomerization of butadiene with methanol and water that is industrially developed, the modification of polyols is still under development. Recently, a series of new substrates has been involved in this reaction, including diols, pure or crude glycerol, protected or unprotected monosaccharides, as well as polysaccharides. This opens up the formation of new products having specific physicochemical properties. We will describe recent advances in this field, focusing on the reaction of renewable products and more specifically on saccharides. The efficient catalytic systems as well as the optimized reaction conditions will be described and some physicochemical properties of the products will be reported.

  18. DFT Investigation of the Palladium-Catalyzed Ene-Yne Coupling

    DEFF Research Database (Denmark)

    Henriksen, Signe Teuber; Tanner, David Ackland; Skrydstrup, T.

    2010-01-01

    ). Concerning chemoselectivity, the calculations also clarify why the ene-yne coupling is able to dominate over plausible alternative reaction pathways such as alkene homocoupiing and alkyne polymerization. The role of the phosphine ligand at various stages of the catalytic cycle has also been delineated....

  19. Formal total syntheses of classic natural product target molecules via palladium-catalyzed enantioselective alkylation

    Directory of Open Access Journals (Sweden)

    Yiyang Liu

    2014-10-01

    Full Text Available Pd-catalyzed enantioselective alkylation in conjunction with further synthetic elaboration enables the formal total syntheses of a number of “classic” natural product target molecules. This publication highlights recent methods for setting quaternary and tetrasubstituted tertiary carbon stereocenters to address the synthetic hurdles encountered over many decades across multiple compound classes spanning carbohydrate derivatives, terpenes, and alkaloids. These enantioselective methods will impact both academic and industrial settings, where the synthesis of stereogenic quaternary carbons is a continuing challenge.

  20. Palladium-Catalyzed Reductive Insertion of Alcohols into Aryl Ether Bonds

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Meng [Institute for Integrated Catalysis, Pacific Northwest National Laboratory, P.O. Box 999 Richland WA 99352 USA; Gutiérrez, Oliver Y. [Institute for Integrated Catalysis, Pacific Northwest National Laboratory, P.O. Box 999 Richland WA 99352 USA; Camaioni, Donald M. [Institute for Integrated Catalysis, Pacific Northwest National Laboratory, P.O. Box 999 Richland WA 99352 USA; Lercher, Johannes A. [Institute for Integrated Catalysis, Pacific Northwest National Laboratory, P.O. Box 999 Richland WA 99352 USA; Department of Chemistry and Catalysis Research Institute, TU München, Lichtenbergstrasse 4 85748 Garching Germany

    2018-03-06

    Pd/C catalyzes C-O bond cleavage of aryl ethers (diphenyl ether and cyclohexyl phenyl ether) by methanol in H2. The aromatic C-O bond is cleaved by reductive methanolysis, which is initiated by Pd-catalyzed partial hydrogenation of one phenyl ring to form an enol ether. The enol ether reacts rapidly with methanol to form a ketal, which generates methoxycyclohexene by eliminating phenol or an alkanol. Subsequent hydrogenation leads to methoxycyclohexane.

  1. Palladium catalyzed direct oxidation of benzene with molecular oxygen to phenol

    International Nuclear Information System (INIS)

    Jintoku, Tetsuro; Takaki, Ken; Fujiwara, Yuzo; Fuchita, Yoshio; Hiraki, Katsuma.

    1990-01-01

    Direct phenol synthesis from benzene is currently one of the most important problems in modern chemistry. We have reported new phenol synthesis from benzene and O 2 via direct activation of a C-H aromatic bond by the Pd(OAc) 2 /phenanthroline catalyst system. The evidence for direct oxidation of benzene by O 2 was obtained using 18 O and 2 H isotopes. The mechanism was proposed on the basis of these results and the reactions of Ph-Pd σ complex intermediates. (author)

  2. Palladium-catalyzed arylation of enoates with iodobenzene: stereoselective synthesis of trisubstituted olefins

    Energy Technology Data Exchange (ETDEWEB)

    Fernandes, Talita de A. [Universidade Federal do Rio de Janeiro (UFRJ/LQB), RJ (Brazil). Nucleo de Pesquisas de Produtos Naturais. Laboratorio de Quimica Bioorganica; Universidade Federal do Rio de Janeiro (UFRJ), RJ (Brazil). Instituto de Quimica. Interlab; Silva, Alcides J.M. da; Costa, Paulo R.R., E-mail: prrcosta2011@gmail.com [Universidade Federal do Rio de Janeiro (UFRJ/LQB), RJ (Brazil). Nucleo de Pesquisas de Produtos Naturais. Laboratorio de Quimica Bioorganica; Esteves, Pierre M. [Universidade Federal do Rio de Janeiro (UFRJ), RJ (Brazil). Instituto de Quimica. Interlab; Eberlin, Marcos N., E-mail: eberlin@iqm.unicamp.br [Universidade Estadual de Campinas (UNICAMP), SP (Brazil). Instituto de Quimica. Laboratorio ThoMSon de Espectrometria de Massas; Vaz, Boniek G. [Universidade Estadual de Campinas (UNICAMP), SP (Brazil). Instituto de Quimica. Laboratorio ThoMSon de Espectrometria de Massas; Universidade Federal de Goias (UFGO), Goiania, GO (Brazil). Instituto de QuImica

    2013-03-15

    The Heck reaction between E- and Z-enoates and iodobenzene was studied in the presence of Pd(OAc){sub 2}. The stereochemistry in resulting adducts was dependent on the enoate geometry (stereospecific reaction). Best yields were obtained from Z-isomers in acetone using Ag{sub 2} CO{sub 3} as base. The main cationic palladium intermediates possibly involved in the catalytic cycle could be intercepted and characterized by electrospray ionization mass spectrometry (ESI-MS). The stereoselectivity observed was rationalized through the classic mechanism of the Heck reaction. (author)

  3. Palladium-catalyzed arylation of enoates with iodobenzene: stereoselective synthesis of trisubstituted olefins

    International Nuclear Information System (INIS)

    Fernandes, Talita de A.; Universidade Federal do Rio de Janeiro; Silva, Alcides J.M. da; Costa, Paulo R.R.; Esteves, Pierre M.; Eberlin, Marcos N.; Vaz, Boniek G.; Universidade Federal de Goias

    2013-01-01

    The Heck reaction between E- and Z-enoates and iodobenzene was studied in the presence of Pd(OAc) 2 . The stereochemistry in resulting adducts was dependent on the enoate geometry (stereospecific reaction). Best yields were obtained from Z-isomers in acetone using Ag 2 CO 3 as base. The main cationic palladium intermediates possibly involved in the catalytic cycle could be intercepted and characterized by electrospray ionization mass spectrometry (ESI-MS). The stereoselectivity observed was rationalized through the classic mechanism of the Heck reaction. (author)

  4. Palladium-catalyzed, asymmetric Baeyer–Villiger oxidation of prochiral cyclobutanones with PHOX ligands

    KAUST Repository

    Petersen, Kimberly S.; Stoltz, Brian M.

    2011-01-01

    and 81% ee. Lactones of enantiopurity ≥93% could be obtained through a single recrystallization step. Importantly, 3,3-disubtituted cyclobutanones produced enantioenriched lactones containing a β-quaternary center. © 2011 Elsevier Ltd. All rights reserved.

  5. Palladium-Catalyzed Anti-Markovnikov Oxidation of Allylic Amides to Protected beta-Amino Aldehydes

    NARCIS (Netherlands)

    Dong, Jiajia; Harvey, Emma C.; Fananas-Mastral, Martin; Browne, Wesley R.; Feringa, Bernard

    2014-01-01

    A general method for the preparation of N-protected beta-amino aldehydes from allylic amines or linear allylic alcohols is described. Here the Pd(II)-catalyzed oxidation of N-protected allylic amines with benzoquinone is achieved in tBuOH under ambient conditions with excellent selectivity toward

  6. S,O-Ligand-Promoted Palladium-Catalyzed C-H Functionalization Reactions of Nondirected Arenes

    NARCIS (Netherlands)

    Naksomboon, K.; Valderas, C.; Gomez-Martinez, M.; Alvarez-Casao, Y.; Fernández Ibáñez, M.A.

    Pd(II)-catalyzed C-H functionalization of non directed arenes has been realized using an inexpensive and easily accessible type of bidentate S,O-ligand. The catalytic system shows high efficiency in the C-H olefination reaction of electron-rich and electron-poor arenes. This methodology is

  7. Memory effects in palladium-catalyzed allylic Alkylations of 2-cyclohexen-1-yl acetate

    DEFF Research Database (Denmark)

    Svensen, Nina; Fristrup, Peter; Tanner, David Ackland

    2007-01-01

    The objective of this work was to characterize the enantiospecificity of the allylic alkylation of enantioenriched 2-cyclohexen-1-yl acetate with the enolate ion of dimethyl malonate catalyzed by unsymmetrical palladium catalysts. The precatalysts employed were (eta(3)-allyl)PdLCl, where L...

  8. Chemistry in Confinement: Copper and Palladium Catalyzed Ecofriendly Organic Transformations within Porous Frameworks.

    Science.gov (United States)

    Kumar, Basuvaraj Suresh; Pitchumani, Kasi

    2018-05-01

    A concise account on the use of transition metals copper (Cu) and palladium (Pd), as their cations as well as nanoparticles exchanged/immobilized onto porous frameworks such as zeolites, metal organic frameworks (MOFs), covalent organic polymers (COPs) and hollow nanostructures, functioning as catalysts in organic synthesis is presented. This biomimetic account, "focusing on catalytic systems in confinement" within zero-dimensional microenvironments and second sphere coordination covers primarily results from our group on N-sulfonylketenimine mediated cycloaddition, hydrogenation and C-C bond forming reactions, thus providing an interesting insight into the versatility and utility of these Cu and Pd catalysts. Other significant advantages and green credentials of confinement such as stability, selectivity, reusability, promotion of multicomponent reactions, use of green solvents, atom economy, and use of ambient conditions are highlighted at appropriate places. In the final section, our views on the current achievements and the future prospects in this area are summarized. © 2018 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Metal concentrations in selected tissues and main prey species of the annulated sea snake (Hydrophis cyanocinctus) in the Hara Protected Area, northeastern coast of the Persian Gulf, Iran

    International Nuclear Information System (INIS)

    Rezaie-Atagholipour, Mohsen; Riyahi-Bakhtiari, Alireza; Sajjadi, Mirmasoud; Yap, Chee Kong; Ghaffari, Sanaz; Ebrahimi-Sirizi, Zohreh; Ghezellou, Parviz

    2012-01-01

    This study is the first detailed ecotoxicological study of the annulated sea snake, Hydrophis cyanocinctus. Concentrations of lead, cadmium, nickel and vanadium were evaluated in muscle, liver, kidney, skin and blood of the annulated sea snake (H. cyanocinctus) and in the whole bodies of its main prey species (Periophthalmus waltoni and Boleophthalmus dussumieri) in the Hara Protected Area, the Persian Gulf. The mean concentrations of lead and vanadium were highest in the kidney, which identified the kidney as a target organ for metals in sea snakes as it is in other reptilian groups. Mean concentrations of cadmium and nickel were highest in the liver and skin, respectively. Mean cadmium concentrations were significantly higher in the liver compared to prey species, which indicated that prey items may be a source of cadmium for the annulated sea snake in the study area. Data presented here may be considered as a baseline for further ecotoxicological studies in sea snakes.

  10. Cobalt-Mediated [3+2]-Annulation Reaction of Alkenes with α,β-Unsaturated Ketones and Imines

    Science.gov (United States)

    Schomaker, Jennifer M.; Toste, F. Dean; Bergman, Robert G.

    2009-01-01

    The utility of cobalt dinitrosyl complexes for the [3+2] annulation of alkenes with unsaturated enones and ketimines has been demonstrated. Reaction of a series of cobalt dinitrosyl/alkene adducts with conjugate acceptors in the presence of Sc(OTf)3/LHMDS formed two new C-C bonds at the carbons α to the nitrosyl groups of the substrate, leading to unusual tri- and tetracycles. Retrocycloaddition of these products in the presence of norbornadiene yielded functionalized tetrasubstituted bicyclic olefins. PMID:19639989

  11. Rhodium-catalyzed annulation of arenes with alkynes through weak chelation-assisted C-H activation.

    Science.gov (United States)

    Yang, Yudong; Li, Kaizhi; Cheng, Yangyang; Wan, Danyang; Li, Mingliang; You, Jingsong

    2016-02-18

    The purpose of this article is to give a brief review of weak chelation-assistance as a powerful means for the rhodium-catalyzed annulation of arenes with alkynes. The use of commonly occurring functional groups (e.g., ketones, aldehydes, carboxylic acids and alcohols) as the directing groups enriches the versatility of auxiliary ligands and extends the scope of products. This short article offers an overview on emerging procedures, highlights their advantages and limitations, and covers the latest progress in the rapid synthesis of organic functional materials and natural products.

  12. Stereodivergent Synthesis of N-Heterocycles by Catalyst-Controlled, Activity-Directed Tandem Annulation of Diazo Compounds with Amino Alkynes.

    Science.gov (United States)

    Liu, Kai; Zhu, Chenghao; Min, Junxiang; Peng, Shiyong; Xu, Guangyang; Sun, Jiangtao

    2015-10-26

    A stereodivergent synthesis of five-membered N-heterocycles, such as 2,3-dihydropyrroles, and 2-methylene and 3-methylene pyrrolidines, has been developed through a tandem annulation of amino alkynes with diazo compounds and involves the trapping of in situ formed intermediates. Mechanistic investigations indicate that the copper-catalyzed tandem annulations proceed by allenoate formation and subsequent intramolecular hydroamination. In contrast, the rhodium-catalyzed protocol features a carbenoid insertion into the NH bond and subsequent Conia-ene cyclization. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Natural Disaster as a Reason to Annul the Nuclear Liability: From National and International Law’s Perspective

    International Nuclear Information System (INIS)

    Taufiq, D.

    2016-01-01

    One serious issue that deserves more attention from Indonesia before constructing its first NPP, regarding its ''ring of fire'' geological position, is the natural disaster as a reason to annul the nuclear liability. Article 32 of Act No 10 Year 1997 on Nuclear Energy stipulates that ''nuclear installation operator shall not be responsible for the damage caused by a nuclear accident that occurred as a direct impact of a domestic or international armed conflict or natural disaster that exceeded the design limits and acceptance criteria set by the regulatory body.'' In its explanation natural disaster includes earthquakes. This article adopts the provision of article IV paragraph 3b 1963 Vienna Convention on Civil Liability for Nuclear Damage. But, in 1997 Amendment Protocol, this provision has been deleted. Natural disasters often referred to as an ''act of god'' because it occurs outside the control of the human. Nevertheless, not all natural disasters could cause the operator to annul its civil liability. The most important question is: ''has the operator taken all necessary preventive actions to prevent accidents, before and during the natural disaster?''

  14. Rh-Catalyzed annulations of N-methoxybenzamides with ketenimines: synthesis of 3-aminoisoindolinones and 3-diarylmethyleneisoindolinones with strong aggregation induced emission properties.

    Science.gov (United States)

    Zhou, Xiaorong; Peng, Zhixing; Zhao, Hongyang; Zhang, Zhiyin; Lu, Ping; Wang, Yanguang

    2016-08-23

    Rhodium-catalyzed C-H activation/annulation reactions of ketenimines with N-methoxybenzamides furnished 3-aminoisoindolin-1-ones and 3-(diarylmethylene)isoindolin-1-ones. The synthesized 3-(diarylmethylene)isoindolin-1-ones exhibited aggregation induced emissions in aqueous tetrahydrofuran solution and strong green-yellow emissions in solids.

  15. Annulation of phenols with methylbutenol over MOFs: The role of catalyst structure and acid strength in producing 2,2-dimethylbenzopyran derivatives

    Czech Academy of Sciences Publication Activity Database

    Shamzhy, Mariya; Opanasenko, Maksym; Garcia, H.; Čejka, Jiří

    2015-01-01

    Roč. 202, JAN 2015 (2015), s. 297-302 ISSN 1387-1811 R&D Projects: GA ČR GA14-07101S Institutional support: RVO:61388955 Keywords : metal -organic frameworks * acid ity * annulation Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.349, year: 2015

  16. A facile synthesis of substituted 2-alkylquinolines through [3+3] annulation between 3-ethoxycyclobutanones and aromatic amines at room temperature.

    Science.gov (United States)

    Shan, Gang; Sun, Xiuyun; Xia, Qian; Rao, Yu

    2011-11-04

    An efficient single-step approach toward the synthesis of 2-alkylquinolines is described. Through a Lewis acid mediated [3+3] annulation reaction between 3-ethoxycyclobutanones and aromatic amines, a variety of multisubstituted 2-alkylquinoline derivatives were prepared regioselectively at room temperature. © 2011 American Chemical Society

  17. Pyridine synthesis by reactions of allyl amines and alkynes proceeding through a Cu(OAc)2 oxidation and Rh(III)-catalyzed N-annulation sequence.

    Science.gov (United States)

    Kim, Dong-Su; Park, Jung-Woo; Jun, Chul-Ho

    2012-11-28

    A new methodology has been developed for the synthesis of pyridines from allyl amines and alkynes, which involves sequential Cu(II)-promoted dehydrogenation of the allylamine and Rh(III)-catalyzed N-annulation of the resulting α,β-unsaturated imine and alkyne.

  18. Synthesis of new annulated pyrano[2,3-d]pyrimidine derivatives using organo catalyst (DABCO in aqueous media

    Directory of Open Access Journals (Sweden)

    Ajmal R. Bhat

    2017-01-01

    Full Text Available A selective method for the synthesis of annulated pyrano[2,3-d]pyrimidines has been developed. It was shown that base catalysis is more efficient in this reaction, rather than acid catalysis as it is believed that 1,4-diazabicyclo[2.2.2]octane (DABCO is N-type base catalyst used for the synthesis of pyrano[2,3-d]pyramidine derivatives via one-pot three component condensation reactions of various aromatic aldehydes, active methylene compounds and barbituric acid in aqueous ethanol carried at normal temperature. The potential application of DABCO in organic synthesis increasing rapidly because of its reaction simplicity, less pollution, and minimum reaction time, high yields of the biological active products, uses less toxic solvents and low cost chemicals.

  19. Pd-catalyzed aerobic oxidative annulation of cyclohexanones and 2-aminophenyl ketones: A direct approach to acridines

    Science.gov (United States)

    Mu, Wanlu; Li, Xiaowei; Wang, Longfei; Chen, Yong; Wu, Yanchao

    2017-08-01

    An efficient aerobic oxidative annulation of cyclohexanones and 2-aminophenyl ketones approach to substituted acridines, a structural motif for a large number of pharmaceuticals and functional materials is described. The key feature of this method is the use of oxygen as the sole oxidant and Pd catalyst, which resulting in the high regioselectivity with unsymmetrical meta-substituted cyclohexanones. The electron gap of the global redox condensation process is filled and the reaction efficiency is significantly promoted by O2 as a redox moderator. This protocol possesses many advantages such as using O2 as a cheap and nonhazardous oxidant, high regioselectivity and water as the only by-product, which meet the principle of green chemistry.

  20. Rhodium(III)-Catalyzed [3+2]/[5+2] Annulation of 4-Aryl 1,2,3-Triazoles with Internal Alkynes through Dual C(sp2)-H Functionalization.

    Science.gov (United States)

    Yang, Yuan; Zhou, Ming-Bo; Ouyang, Xuan-Hui; Pi, Rui; Song, Ren-Jie; Li, Jin-Heng

    2015-05-26

    A rhodium(III)-catalyzed [3+2]/[5+2] annulation of 4-aryl 1-tosyl-1,2,3-triazoles with internal alkynes is presented. This transformation provides straightforward access to indeno[1,7-cd]azepine architectures through a sequence involving the formation of a rhodium(III) azavinyl carbene, dual C(sp(2))-H functionalization, and [3+2]/[5+2] annulation. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. A phosphine mediated sequential annulation process of 2-tosylaminochalcones with MBH carbonates to construct functionalized aza-benzobicyclo[4.3.0] derivatives.

    Science.gov (United States)

    Zhang, Qinglong; Zhu, Yannan; Jin, Hongxing; Huang, You

    2017-04-04

    A novel phosphine mediated sequential annulation process to construct functionalized aza-benzobicyclo[4.3.0] derivatives has been developed involving a one-pot sequential catalytic and stoichiometric process, which generates a series of benzobicyclo[4.3.0] compounds containing one quaternary center with up to 94% yield and 20 : 1 dr value. In this reaction, MBH carbonates act as 1,2,3-C 3 synthons.

  2. PRACTICAL ASPECTS REGARDING THE CLAIM FOR THE ANNULMENT OF THE RESOLUTIONS OF THE GENERAL MEETING OF SHAREHOLDERS, FROM A SUBSTANTIAL AND PROCEDURAL PERSPECTIVE

    Directory of Open Access Journals (Sweden)

    Roxana - Mihaela CATEA

    2017-05-01

    Full Text Available The purpose of this paper is to provide a brief analysis of the legal framework regarding the procedural and substantial dispositions governing the claim for the annulment of the resolutions of the general meeting of shareholders. The main objective is to render a practical tool both to stakeholders and third parties who are interested in the legal means available for blocking the implementation of any measures which are contrary to the company’s interest. Further to the amendments brought through the New Civil Procedural Code, the claim for annulment of the resolutions of the general assembly must be analyzed from a procedural point of view, as well as from a substantial standpoint. The shareholders must be aware of the grounds for challenging a general assembly's resolution to properly safeguard their rights. One common issue which is invoked as grounds for annulment is the abuse of majority of the majority shareholder. However, the difficulty of alleging such a reason is left to practitioners. Therefore, its application, although not wide, is highly imaginative.

  3. N-Annulated perylene substituted zinc–porphyrins with different linking modes and electron acceptors for dye sensitized solar cells

    KAUST Repository

    Luo, Jie

    2016-05-03

    Three new N-annulated perylene (NP) substituted porphyrin dyes WW-7-WW-9 with different linking modes and accepting groups were synthesized and applied in Co(ii)/(iii) based dye sensitized solar cells (DSCs). The bay-linked porphyrins WW-7 and WW-8 exhibited moderate power conversion efficiency (PCE = 4.4% and 4.8%, respectively), while the peri-linked porphyrin dye WW-9 showed a PCE up to 9.2% which is slightly lower than that of our reference dye WW-6. Detailed physical measurements (optical and electrochemical), DFT calculations, and photovoltaic characterizations were performed to understand how the structural changes affect their light-harvesting ability, molecular orbital profile, energy level alignment, and eventually the photovoltaic performance. It turned out that the lower efficiencies of the cells based on WW-7 and WW-8 could be ascribed to the weak π-conjugation between the bay-substituted NP and phenylethynyl substituted porphyrin unit. The introduction of a benzothiadiazole acceptor at the anchoring group has induced a significant red shift of the IPCE action spectra of WW-8 and WW-9, by about 90 nm and 50 nm as compared to that of WW-7 and WW-6, respectively. However, less efficient electron injection was observed. Our studies gave some insight into the important role of electronic interactions between different components when one designs a dye for high-efficiency DSCs. © The Royal Society of Chemistry 2016.

  4. Mechanism and Regioselectivity of Rh(III)-Catalyzed Intermolecular Annulation of Aryl-Substituted Diazenecarboxylates and Alkenes: DFT Insights

    KAUST Repository

    Ajitha, Manjaly John

    2016-02-05

    The mechanism of Rh-catalyzed intermolecular annulation of aryl-substituted diazenecarboxylates and alkenes was investigated using density functional theory (DFT) (PCM-M062X/6-311+G(d,p)//M062X/6-31G(d)). The acetate ligand (OAc)-assisted C-H activation via the formation of a five-membered rhodacycle (I-TS1; ΔG‡ = 19.4 kcal/mol) is more favorable compared to that via a four-membered intermediate (II-TS1; ΔG‡ = 27.8 kcal/mol). Our results also revealed that the seven-membered intermediate (I-3, ΔGrel = -6.8 kcal/mol) formed after the alkene insertion could undergo a coordination switch with the adjacent nitrogen atom (via TScs; ΔG‡ = 16.5 kcal/mol) to produce a thermodynamically stable six-membered intermediate (II-3, ΔGrel = -10.4 kcal/mol), eventually leading to a cyclization process followed by a barrierless ligand-assisted protonation to yield the final product. The β-hydride elimination product was found to be kinetically and thermodynamically undesirable. The rate-determining step is identified as the initial C-H activation, consistent with the previous kinetic studies. Notably, DFT studies offered important insights on the ability of the substrate (diazene carboxylate) to promote the switchable coordination site selectivity during the reaction to achieve a lower energy pathway. © 2016 American Chemical Society.

  5. C-H Activation and Alkyne Annulation via Automatic or Intrinsic Directing Groups: Towards High Step Economy.

    Science.gov (United States)

    Zheng, Liyao; Hua, Ruimao

    2018-06-01

    Direct transformation of carbon-hydrogen bond (C-H) has emerged to be a trend for construction of molecules from building blocks with no or less prefunctionalization, leading high atom and step economy. Directing group (DG) strategy is widely used to achieve higher reactivity and selectivity, but additional steps are usually needed for installation and/or cleavage of DGs, limiting step economy of the overall transformation. To meet this challenge, we proposed a concept of automatic DG (DG auto ), which is auto-installed and/or auto-cleavable. Multifunctional oxime and hydrazone DG auto were designed for C-H activation and alkyne annulation to furnish diverse nitrogen-containing heterocycles. Imidazole was employed as an intrinsic DG (DG in ) to synthesize ring-fused and π-extended functional molecules. The alkyne group in the substrates can also be served as DG in for ortho-C-H activation to afford carbocycles. In this account, we intend to give a review of our progress in this area and brief introduction of other related advances on C-H functionalization using DG auto or DG in strategies. © 2018 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. An Analysis of the Constitutional Court Ruling on the Annulment of the Provisions on Coastal Water Concessions (HP-3

    Directory of Open Access Journals (Sweden)

    M. Riza Damanik

    2013-05-01

    Full Text Available After the annulment of the Coastal Water Concessions (HP-3 in 16 June 2011, traditional fisher folk organization leaders found a great fighting spirit to further follow-up the Constitutional Court Ruling to support their daily lives. For those who are being “evicted” from their living space (the coastal waters, they want to reclaim their rights through constitutional ways. Likewise, those who (feel to have lost their existence as Indonesian traditional fisher folk are impatient to find out whether there is a breakthrough in the Constitutional Court Ruling that can restore the fisher folk’s family way of life. The ruling itself was complex and not easy to understand: 169 pages, with complex writing systematic and typical legal language. For this reason, the analysis of the Constitutional Court Ruling regarding the Judicial Review on Law No. 27 of 2007 on the Management of Coastal Areas and Small Islands was necessary in order to provide a simpler representation of the Constitutional Court Ruling, and one that is expected to trigger a constructive discussion to implement the favorable parts of the decree for the greatest welfare of the people.

  7. N-Annulated perylene substituted zinc–porphyrins with different linking modes and electron acceptors for dye sensitized solar cells

    KAUST Repository

    Luo, Jie; Zhang, Jing; Huang, Kuo-Wei; Qi, Qingbiao; Dong, Shaoqiang; Zhang, Jie; Wang, Peng; Wu, Jishan

    2016-01-01

    Three new N-annulated perylene (NP) substituted porphyrin dyes WW-7-WW-9 with different linking modes and accepting groups were synthesized and applied in Co(ii)/(iii) based dye sensitized solar cells (DSCs). The bay-linked porphyrins WW-7 and WW-8 exhibited moderate power conversion efficiency (PCE = 4.4% and 4.8%, respectively), while the peri-linked porphyrin dye WW-9 showed a PCE up to 9.2% which is slightly lower than that of our reference dye WW-6. Detailed physical measurements (optical and electrochemical), DFT calculations, and photovoltaic characterizations were performed to understand how the structural changes affect their light-harvesting ability, molecular orbital profile, energy level alignment, and eventually the photovoltaic performance. It turned out that the lower efficiencies of the cells based on WW-7 and WW-8 could be ascribed to the weak π-conjugation between the bay-substituted NP and phenylethynyl substituted porphyrin unit. The introduction of a benzothiadiazole acceptor at the anchoring group has induced a significant red shift of the IPCE action spectra of WW-8 and WW-9, by about 90 nm and 50 nm as compared to that of WW-7 and WW-6, respectively. However, less efficient electron injection was observed. Our studies gave some insight into the important role of electronic interactions between different components when one designs a dye for high-efficiency DSCs. © The Royal Society of Chemistry 2016.

  8. Pyrroloindolone synthesis via a Cp*Co(III)-catalyzed redox-neutral directed C-H alkenylation/annulation sequence.

    Science.gov (United States)

    Ikemoto, Hideya; Yoshino, Tatsuhiko; Sakata, Ken; Matsunaga, Shigeki; Kanai, Motomu

    2014-04-09

    A unique synthetic utility of a Cp*Co(III) catalyst in comparison with related Cp*Rh(III) catalysts is described. A C2-selective indole alkenylation/annulation sequence proceeded smoothly with catalytic amount of a [Cp*Co(III)(C6H6)](PF6)2 complex and KOAc. Intramolecular addition of an alkenyl-Cp*Co species to a carbamoyl moiety gave pyrroloindolones in 58-89% yield in one pot. Clear difference was observed between the catalytic activity of the Cp*Co(III) complex and those of Cp*Rh(III) complexes, highlighting the unique nucleophilic activity of the organocobalt species. The Cp*Co(III) catalysis was also suitable for simple alkenylation process of N-carbamoyl indoles, and broad range of alkynes, including terminal alkynes, were applicable to give C2-alkenylated indoles in 50-99% yield. Mechanistic studies on C-H activation step under Cp*Co(III) catalysis with the aid of an acetate unit as well as evaluation of the difference between organo-Co(III) species and organo-Rh(III) species are also described.

  9. Jurisprudential aspects regarding the action in annulment of the debtor’s patrimonial transfers, the debtor being in insolvency procedure

    Directory of Open Access Journals (Sweden)

    Angela MIFF

    2015-06-01

    Full Text Available The study aims to present relevant aspects from the jurisprudential solutions of the High Court of Cassation and Justice in matters of the action in annulment of the patrimonial transfers of the debtor in insolvency procedure and of other judicial actions introduced by the procedure bodies or, by case, the participants to the procedure who are enabled to use the measures prescribed by the law for the purpose of restoring the debtor’s patrimony. The jurisprudential solutions adopted under the incidence of the former Law no.85/2006 on the insolvency procedure represent, in present, under diverse aspects, elements of continuity with the principles and rules established by the new law in this matter. Law no.85/2014 on the prevention insolvency procedures and of insolvency establishes the legal frame for the exertion of the measures having as purpose the restoration, in the debtor’s patrimony, of certain assets, transferred by the debtor to the fraud of the creditors’ interests, or of their value, in the scope of covering the passive part to satisfy the creditors’ interests. The new law continues the tradition of the former regulations in this matter but, also, brings some novelty elements such as the decrease or, in some cases, the increase of the duration of certain terms that the exertion of the mentioned judicial actions or their object refer to or the completion of the category of the persons entitled to introduce the mentioned judicial actions with the creditor who holds more than 50% of the value of the claims enlisted in the amount of claims.

  10. DFT/TDDFT study on the electronic structure and spectral properties in annulated analogue of phenyl heteroazulene derivative

    International Nuclear Information System (INIS)

    Gasiorski, P.; Danel, K.S.; Matusiewicz, M.; Uchacz, T.; Kuźnik, W.; Piatek, Ł.; Kityk, A.V.

    2012-01-01

    Highlights: ► Cyclic voltammetry study of heteroazulene derivative PTNA. ► DFT/TDDFT/PCM calculations of molecular geometry and electronic states in PTNA. ► TDDFT/PCM calculations of the absorption and fluorescence spectra in PTNA. ► Comparison between TDDFT/PCM calculated and measured optical spectra. - Abstract: Paper reports the DFT/TDDFT study on the electronic structure and spectral properties of the seven-membered annulated heteroazulene derivative 6-phenyl-6H-5,6,7-triazadibenzo[f,h]naphtho[3,2,1-cd]azulene (PTNA) by means of polarizable continuum model (PCM) and Lippert–Mataga–Onsager reaction field (LM-ORF) model at the B3LYP/6-31+G(d,p) level of theory. The results of calculations are compared with the measured optical absorption and fluorescence spectra as well as with the cyclic voltammetry data. The DFT/TDDFT methods exhibit rather good quantitative agreement regarding the spectral position of the first absorption band; the discrepancy between the experiment and theory is less than 0.1 eV. As for the fluorescence emission the TDDFT calculations underestimate the transition energy of about 0.45 eV. The discrepancy should be attributed to insufficient accuracy of the TDDFT optimization in the excited state. In the polar solvent environment, all the TDDFT/PCM approaches give the bathochromic (red) shift for the fluorescence emission and the hypsochromic (blue) shift for the optical absorption in accordance with the experimental observation. As for the fluorescence emission fairly good agreement with the experiment provides the hybrid approach being the combination of the TDDFT/PCM optimization with the semiempirical electronic structure calculations by PM3 method and solvation LM-ORF model predicting the emission energy in different solvents with the accuracy better than 0.06 eV.

  11. A Unique (3+2) Annulation Reaction between Meldrum's Acid and Nitrones: Mechanistic Insight by ESI-IMS-MS and DFT Studies.

    Science.gov (United States)

    Lespes, Nicolas; Pair, Etienne; Maganga, Clisy; Bretier, Marie; Tognetti, Vincent; Joubert, Laurent; Levacher, Vincent; Hubert-Roux, Marie; Afonso, Carlos; Loutelier-Bourhis, Corinne; Brière, Jean-François

    2018-03-15

    The fragile intermediates of the domino process leading to an isoxazolidin-5-one, triggered by unique reactivity between Meldrum's acid and an N-benzyl nitrone in the presence of a Brønsted base, were determined thanks to the softness and accuracy of electrospray ionization mass spectrometry coupled to ion mobility spectrometry (ESI-IMS-MS). The combined DFT study shed light on the overall organocatalytic sequence that starts with a stepwise (3+2) annulation reaction that is followed by a decarboxylative protonation sequence encompassing a stereoselective pathway issue. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. 1,4-Iron Migration for Expedient Allene Annulations through Iron-Catalyzed C-H/N-H/C-O/C-H Functionalizations.

    Science.gov (United States)

    Mo, Jiayu; Müller, Thomas; Oliveira, João C A; Ackermann, Lutz

    2018-06-25

    C-H activation bears great potential for enabling sustainable molecular syntheses in a step- and atom-economical manner, with major advances having been realized with precious 4d and 5d transition metals. In contrast, we employed earth abundant, nontoxic iron catalysts for versatile allene annulations through a unique C-H/N-H/C-O/C-H functionalization sequence. The powerful iron catalysis occurred under external-oxidant-free conditions even at room temperature, while detailed mechanistic studies revealed an unprecedented 1,4-iron migration regime for facile C-H activations. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Palladium-catalyzed asymmetric alkylation in the synthesis of cyclopentanoid and cycloheptanoid core structures bearing all-carbon quaternary stereocenters

    KAUST Repository

    Hong, Allen Y.

    2011-12-01

    General catalytic asymmetric routes toward cyclopentanoid and cycloheptanoid core structures embedded in numerous natural products have been developed. The central stereoselective transformation in our divergent strategies is the enantioselective decarboxylative alkylation of seven-membered β-ketoesters to form α-quaternary vinylogous esters. Recognition of the unusual reactivity of β-hydroxyketones resulting from the addition of hydride or organometallic reagents enabled divergent access to γ-quaternary acylcyclopentenes through a ring contraction pathway or γ-quaternary cycloheptenones through a carbonyl transposition pathway. Synthetic applications of these compounds were explored through the preparation of mono-, bi-, and tricyclic derivatives that can serve as valuable intermediates for the total synthesis of complex natural products. This work complements our previous work with cyclohexanoid systems.

  14. Synthesis of novel carbazole derived substances using some organoboron compounds by palladium catalyzed and investigation of its semiconductor device characteristics

    Science.gov (United States)

    Gorgun, Kamuran; Caglar, Yasemin

    2018-04-01

    Carbazole compounds in particular represent one of the most intensely used and studied class of semiconducting materials. In this study, considering the information given in the literature the Ullman and Suzuki-Miyaura coupling reaction were carried out using carbazole, 1,4-dibromobenzene and pyrene-1-boronic acid. The synthesized carbazole derivatives are characterized by 1H NMR and elemental analysis. The spectroscopic and thermal properties of the synthesized novel carbazole derivative 9-(4-(pyren-4-yl)phenyl)-9H-carbazole (Cz-py) were investigated. And also, the n-Si/p-Cz:py heterojunction diode was fabricated. The electrical properties of this diode were characterized by current-voltage (I-V) and capacitance-voltage (C-V) measurements.

  15. Optimization of Palladium-Catalyzed In Situ Destruction of Trichloroehtylene-Contaminated Groundwater Using a Genetic Algorithm

    National Research Council Canada - National Science Library

    Fernandez, Manuel

    2001-01-01

    .... In this study, objective and fitness functions, based on system costs and TCE concentration requirements, were developed to optimize a dual-well HFTW system with in-well Pd/Al reactors in a two...

  16. Ketenimines from Isocyanides and Allyl Carbonates: Palladium-Catalyzed Synthesis of β,γ-Unsaturated Amides and Tetrazoles.

    Science.gov (United States)

    Qiu, Guanyinsheng; Mamboury, Mathias; Wang, Qian; Zhu, Jieping

    2016-12-05

    The reaction of allyl ethyl carbonates with isocyanides in the presence of a catalytic amount of Pd(OAc) 2 provided ketenimines through β-hydride elimination of the allyl imidoylpalladium intermediates. The insertion of the isocyanide into the π-allyl Pd complex proceeded via an unusual η 1 -allyl Pd species. The resulting ketenimines were hydrolyzed to β,γ-unsaturated carboxamides during purification by flash column chromatography on silica gel or converted in situ into 1,5-disubstituted tetrazoles by [3+2] cycloaddition with hydrazoic acid or trimethylsilyl azide. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. An intramolecular [2 + 2] cycloaddition of ketenimines via palladium-catalyzed rearrangements of N-allyl-ynamides.

    Science.gov (United States)

    DeKorver, Kyle A; Hsung, Richard P; Song, Wang-Ze; Wang, Xiao-Na; Walton, Mary C

    2012-06-15

    A cascade of Pd-catalyzed N-to-C allyl transfer-intramolecular ketenimine-[2 + 2] cycloadditions of N-allyl ynamides is described. This tandem sequence is highly stereoselective and the [2 + 2] cycloaddition could be rendered in a crossed or fused manner depending on alkene substitutions, leading to bridged and fused bicycloimines.

  18. Formation of Ketenimines via the Palladium-Catalyzed Decarboxylative π-Allylic Rearrangement of N-Alloc Ynamides.

    Science.gov (United States)

    Alexander, Juliana R; Cook, Matthew J

    2017-11-03

    A new approach for the formation of ketenimines via a decarboxylative allylic rearrangement pathway that does not require strong stabilizing or protecting groups has been developed. The products can be readily hydrolyzed into their corresponding secondary amides or reacted with sulfur ylides to perform an additional [2,3]-Wittig process. Mechanistic studies suggest an outer-sphere process in which reductive alkylation is rate-limiting.

  19. Palladium-Catalyzed ortho C-H Arylation of Benzaldehydes Using ortho-Sulfinyl Aniline Transient Auxiliary.

    Science.gov (United States)

    Mu, Delong; He, Gang; Chen, Gong

    2018-05-03

    A PdII-catalyzed ortho-(Csp2)-H arylation reaction of benzaldehydes using catalytic amount of 2-methylsulfinyl-aniline as transient auxiliary was developed. This reaction is compatible with a broad range of benzaldehyde and aryl iodide substrates. Compared with other related reaction systems, an excellent regioselectivity for ortho-C(sp2)-H bonds over benzylic C(sp3)-H bonds was obtained for ortho-alkyl-benzaldehyde substrates. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Ex Situ Generation of Stoichiometric and Substoichiometric 12CO and 13CO and Its Efficient Incorporation in Palladium Catalyzed Aminocarbonylations

    DEFF Research Database (Denmark)

    Hermange, Philippe; Lindhardt, Anders Thyboe; Taaning, Rolf Hejle

    2011-01-01

    to the development of a new solid, stable, and easy to handle source of CO for chemical transformations. The synthesis of this CO-precursor also provided an entry point for the late installment of an isotopically carbon-labeled acid chloride for the subsequent release of gaseous [13C]CO. In combination with studies...... is safely handled and stored. Furthermore, since the CO is generated ex situ, excellent functional group tolerance is secured in the carbonylation chamber. Finally, CO is only generated and released in minute amounts, hence, eliminating the need for specialized equipment such as CO-detectors and equipment...

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

    KAUST Repository

    Ebner, David C.; Bagdanoff, Jeffrey T.; Ferreira, Eric M.; McFadden, Ryan; Caspi, Daniel D.; Trend, Raissa M.; Stoltz, Brian M.

    2010-01-01

    ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

  2. Combined experimental and theoretical study of the mechanism and enantioselectivity of palladium-catalyzed intermolecular Heck coupling

    DEFF Research Database (Denmark)

    Henriksen, Signe Teuber; Norrby, Per-Ola; Kaukoranta, Päivi

    2008-01-01

    . The steric interactions in this transition state fully account for the enantioselectivity observed with the ligands studied. The calculations also predict relative reactivity and nonlinear mixing effects for the investigated ligands; these predictions are fully validated by experimental testing. Finally......The asymmetric Heck reaction using P,N-ligands has been studied by a combination of theoretical and experimental methods. The reaction follows Halpern-style selectivity; that is, the major isomer is produced from the least favored form of the pre-insertion intermediate. The initially formed Ph......, the low conversion observed with some catalysts was found to be caused by inactivation due to weak binding of the ligand to Pd(0). Adding monodentate PPh3 alleviated the precipitation problem without deteriorating the enantioselectivity and led to one of the most effective catalytic systems to date....

  3. Mono and bimetallic nanoparticles of gold, silver and palladium-catalyzed NADH oxidation-coupled reduction of Eosin-Y

    Science.gov (United States)

    Santhanalakshmi, J.; Venkatesan, P.

    2011-02-01

    Mono metallic (Au, Ag, Pd) and bimetallic (Au-Ag, Ag-Pd, Au-Pd) with 1:1 mol stoichiometry, nanoparticles are synthesized using one-pot, temperature controlled chemical method using cetyltrimethylammonium bromide (CTAB) as the capping agent. The particle sizes (Au = 5.6, Ag = 5.0, Pd = 6.0, Au-Ag = 9.2, Ag-Pd = 9.6, Au-Pd = 9.4 nm) are characterized by UV-Vis, HRTEM, and XRD measurements, respectively. CTAB bindings onto mono and bimetallic nanoparticles are analyzed by FTIR spectra. The catalytic activities of mono and bimetallic nanoparticles are tested on the reaction between NADH oxidation and Eosin-Y reduction. The effects of base, pH, ionic strength, nature of mono and bimetallic catalysts are studied and the reaction conditions are optimized. Bimetallic nanoparticles exhibited better catalysis than the mono metallic nanoparticles, which may be due to the electronic effects of the core to shell metal atoms.

  4. Mono and bimetallic nanoparticles of gold, silver and palladium-catalyzed NADH oxidation-coupled reduction of Eosin-Y

    International Nuclear Information System (INIS)

    Santhanalakshmi, J.; Venkatesan, P.

    2011-01-01

    Mono metallic (Au, Ag, Pd) and bimetallic (Au–Ag, Ag–Pd, Au–Pd) with 1:1 mol stoichiometry, nanoparticles are synthesized using one-pot, temperature controlled chemical method using cetyltrimethylammonium bromide (CTAB) as the capping agent. The particle sizes (Au = 5.6, Ag = 5.0, Pd = 6.0, Au–Ag = 9.2, Ag–Pd = 9.6, Au–Pd = 9.4 nm) are characterized by UV–Vis, HRTEM, and XRD measurements, respectively. CTAB bindings onto mono and bimetallic nanoparticles are analyzed by FTIR spectra. The catalytic activities of mono and bimetallic nanoparticles are tested on the reaction between NADH oxidation and Eosin-Y reduction. The effects of base, pH, ionic strength, nature of mono and bimetallic catalysts are studied and the reaction conditions are optimized. Bimetallic nanoparticles exhibited better catalysis than the mono metallic nanoparticles, which may be due to the electronic effects of the core to shell metal atoms.Graphical Abstract

  5. Molecular-weight-enlarged multiple-pincer ligands: synthesis and application in palladium-catalyzed allylic substitution reactions

    NARCIS (Netherlands)

    Ronde, N.J.; Totev, D.; Müller, Christian; Lutz, M.; Spek, A.L.; Vogt, D.

    2009-01-01

    Three different pincer ligand systems are synthesized via nucleophilic substitution reactions of polyaromatic benzyl bromides as support molecules and phenol derivatives as ligand precursors. Retention tests using a polymeric nanofiltration membrane show moderate to good retention in THF and CH2Cl2.

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

    KAUST Repository

    Ebner, David C.

    2010-03-30

    ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

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

    Directory of Open Access Journals (Sweden)

    İsmail Özdemir

    2010-01-01

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

  8. An efficient protocol for copper-free palladium-catalyzed Sonogashira cross-coupling in aqueous media at low temperatures

    KAUST Repository

    Marziale, Alexander N.; Schlü ter, Johannes; Eppinger, Jö rg

    2011-01-01

    A thorough study on copper-free Sonogashira cross-couplings in water was carried out using the palla-dacycle, [{Pd(μ-Cl){K2-P,C-P(iPr) 2(OC6H3-2-Ph)}}2] as pre-catalyst with different bases and palladium concentrations. The highly active pre

  9. Palladium-catalyzed aryl amination-heck cyclization cascade: A one-flask approach to 3-substituted Indoles

    DEFF Research Database (Denmark)

    Jensen, Thomas; Pedersen, Henrik; Bang-Andersen, B.

    2008-01-01

    Two for the price of one: A Pd/dppf-based catalyst provides access to the title compounds from 1,2-dihalogenated aromatic compounds and allylic amines in a single reaction flask. The initial aryl amination step occurs with excellent selectivity for the aryl iodide to ensure the formation of a sin......Two for the price of one: A Pd/dppf-based catalyst provides access to the title compounds from 1,2-dihalogenated aromatic compounds and allylic amines in a single reaction flask. The initial aryl amination step occurs with excellent selectivity for the aryl iodide to ensure the formation...

  10. An efficient protocol for copper-free palladium-catalyzed Sonogashira cross-coupling in aqueous media at low temperatures

    KAUST Repository

    Marziale, Alexander N.

    2011-11-01

    A thorough study on copper-free Sonogashira cross-couplings in water was carried out using the palla-dacycle, [{Pd(μ-Cl){K2-P,C-P(iPr) 2(OC6H3-2-Ph)}}2] as pre-catalyst with different bases and palladium concentrations. The highly active pre-catalyst imparts good to near quantitative yields using a concentration of 0.25 mol % at 40 °C. This broadly applicable protocol exhibits high tolerance of functional groups and substitution patterns. © 2011 Elsevier Ltd. All rights reserved.

  11. Palladium-Catalyzed Decarboxylative γ-Olefination of 2,5-Cyclohexadiene-1-carboxylic Acid Derivatives with Vinyl Halides.

    Science.gov (United States)

    Chang, Chi-Hao; Chou, Chih-Ming

    2018-04-06

    This study explores a Pd-catalyzed decarboxylative Heck-type Csp 3 -Csp 2 coupling reaction of 2,5-cyclohexadiene-1-carboxylic acid derivatives with vinyl halides to provide γ-olefination products. The olefinated 1,3-cyclohexadienes can be further oxidized to produce meta-alkylated stilbene derivatives. Additionally, the conjugated diene products can also undergo a Diels-Alder reaction to produce a bicyclo[2.2.2]octadiene framework.

  12. Palladium-Catalyzed Enantioselective C-H Olefination of Diaryl Sulfoxides through Parallel Kinetic Resolution and Desymmetrization.

    Science.gov (United States)

    Zhu, Yu-Chao; Li, Yan; Zhang, Bo-Chao; Zhang, Feng-Xu; Yang, Yi-Nuo; Wang, Xi-Sheng

    2018-03-07

    The first example of Pd II -catalyzed enantioselective C-H olefination with non-chiral or racemic sulfoxides as directing groups was developed. A variety of chiral diaryl sulfoxides were synthesized with high enantioselectivity (up to 99 %) through both desymmetrization and parallel kinetic resolution (PKR). This is the first report of Pd II -catalyzed enantioselective C(sp 2 )-H functionalization through PKR, and it represents a novel strategy to construct sulfur chiral centers. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Palladium-catalyzed Asymmetric Hydrosilylation of Styrene and Its Derivatives with Chiral Phosphoramidite Ligands Containing Chiral Ferrocenyl Amine

    Energy Technology Data Exchange (ETDEWEB)

    Park, Hyun-Sub; Kim, Min Young; Ahn, Hyo Jin; Han, Jin Wook [Hanyang University, Seoul (Korea, Republic of)

    2016-06-15

    Asymmetric hydrosilylation was one of the most effective methods, which provided optically active organosilanes as a synthetically useful intermediate in organic synthesis. One useful transformation is the Tamao-Fleming oxidation, which is an oxidation reaction of carbon[BOND]silicone bond to afford optically active alcohols with retention of configuration. It is demonstrated that a palladium catalyst coordinating with phosphoramidite ligand (S {sub a},R {sub c},R {sub c,})-L3a from (S)-BINOL and chiral bis((R)-1-ferrocenylethyl) amine shows a high catalytic activity and enantioselectivity up to 97% ee in asymmetric hydrosilylation of styrene and its derivatives. The hydrosilylation of various olefin substrates using these ligands is in progress.

  14. Indium-Catalyzed Annulation of o-Acylanilines with Alkoxyheteroarenes: Synthesis of Heteroaryl[b]quinolines and Subsequent Transformation to Cryptolepine Derivatives

    Directory of Open Access Journals (Sweden)

    Kyohei Yonekura

    2018-04-01

    Full Text Available We disclose herein the first synthetic method that is capable of offering heteroaryl[b]quinolines (HA[b]Qs with structural diversity, which include tricyclic and tetracyclic structures with (benzothienyl, (benzofuranyl, and indolyl rings. The target HA[b]Q is addressed by the annulation of o-acylanilines and MeO–heteroarenes with the aid of an indium Lewis acid that effectively works to make two different types of the N–C and C–C bonds in one batch. A series of indolo[3,2-b]quinolines prepared here can be subsequently transformed to structurally unprecedented cryptolepine derivatives. Mechanistic studies showed that the N–C bond formation is followed by the C–C bond formation. The indium-catalyzed annulation reaction thus starts with the nucleophilic attack of the NH2 group of o-acylanilines to the MeO-connected carbon atom of the heteroaryl ring in an SNAr fashion, and thereby the N–C bond is formed. The resulting intermediate then cyclizes to make the C–C bond through the nucleophilic attack of the heteroaryl-ring-based carbon atom to the carbonyl carbon atom, providing the HA[b]Q after aromatizing dehydration.

  15. N -annulated perylene as an efficient electron donor for porphyrin-based dyes: Enhanced light-harvesting ability and high-efficiency Co(II/III)-based dye-sensitized solar cells

    KAUST Repository

    Luo, Jie; Xu, Mingfei; Li, Renzhi; Huang, Kuo-Wei; Jiang, Changyun; Qi, Qingbiao; Zeng, Wangdong; Zhang, Jie; Chi, Chunyan; Wang, Peng; Wu, Jishan

    2014-01-01

    Porphyrin-based dyes recently have become good candidates for dye-sensitized solar cells (DSCs). However, the bottleneck is how to further improve their light-harvesting ability. In this work, N-annulated perylene (NP) was used to functionalize

  16. Bisindeno-annulated pentacenes with exceptionally high photo-stability and ordered molecular packing: Simple synthesis by a regio-selective Scholl reaction

    KAUST Repository

    Naibi Lakshminarayana, Arun; Chang, Jingjing; Luo, Jie; Zheng, Bin; Huang, Kuo-Wei; Chi, Chunyan

    2015-01-01

    Bisindeno-annulated pentacenes 3a and 3b were synthesized by a simple regio-selective, FeCl3-mediated Scholl reaction from the corresponding 6,13-diaryl pentacene precursors. The fusion of two indeno-units dramatically changes the electronic properties and chemical reactivity of pentacene and the obtained compounds exhibited exceptionally high photo-stability in the solution, with a half-life time of 11.2 (3a) and 32.0 (3b) days under ambient light and air conditions. Ordered molecular packing with a small π-π stacking distance was observed in the single crystals of 3a and 3b. Our research provides a promising strategy to access stable higher order acenes with controlled molecular order. This journal is

  17. Exceedingly facile one-pot protocols to the synthesis of pyrimido annulated analogues of carbazolo condensed azepinones and their evaluation for analgesic activity

    Directory of Open Access Journals (Sweden)

    M. Agrawal

    2017-07-01

    Full Text Available Extremely simple protocols based on the reactivity of corresponding oxoketenedithioacetal (4, 2-(dimethylaminomethylene ketone (5, β-oxoenolether (6 and α,β-unsaturated ketone (7 derivatives of 7-ethyl-3, 4-dihydroazepino[3,2-b]carbazol-2,5(1H,7H-dione (3 have been developed to provide an easy access to their pyrimido annulated analogues (8-15 of medicinal interest. The key compound 3 from which, the synthesis proceeded has been realized in two steps from the commercial 3-amino-9-ethyl carbazole (1 on its reaction in the first step with ethyl succinyl chloride followed by cyclocondensation of the resulting ester 2 with PPA. The selected synthesized compounds were screened for in-vivo analgesic activity using acetic acid induced writhing model in mice. Among them, compound 13was found to be most active and found comparable to standard aspirin.

  18. Dual overcharge protection and solid electrolyte interphase-improving action in Li-ion cells containing a bis-annulated dialkoxyarene electrolyte additive

    Science.gov (United States)

    Zhang, Jingjing; Shkrob, Ilya A.; Assary, Rajeev S.; Zhang, Shuo; Hu, Bin; Liao, Chen; Zhang, Zhengcheng; Zhang, Lu

    2018-02-01

    1,4-Dialkoxybenzene additives are commonly used as redox active shuttles in lithium-ion batteries in order to prevent runaway oxidation of electrolyte when overcharge conditions set in. During this action the shuttle molecule goes through a futile cycle, becoming oxidized at the cathode and reduced at the anode. Minimizing parasitic reactions in all states of charge is paramount for sustained protective action. Here we demonstrate that recently developed bis-annulated 9,10-bis(2-methoxyethoxy)-1,2,3,4,5,6,7,8-octahydro-1,4:5,8-dimethano-anthracene shuttle molecule (that yields exceptionally stable radical cations) survives over 120 cycles of overcharge abuse with 100% overcharge ratio at C/5 rate. Equally remarkably, in the presence of this additive the cell impedance becomes significantly lower compared to the control cells without the additive; this decrease is observed during the formation, normal cycling, and even under overcharge conditions. This unusual dual action has not been observed in other redox shuttle systems, and it presents considerable practical interest.

  19. N-Annulated perylene-substituted and fused porphyrin dimers with intense near-infrared one-photon and two-photon absorption

    KAUST Repository

    Luo, Jie

    2015-01-21

    Fusion of two N-annulated perylene (NP) units with a fused porphyrin dimer along the S0-S1 electronic transition moment axis has resulted in new near-infrared (NIR) dyes 1a/1b with very intense absorption (ε>1.3×105M-1cm-1) beyond 1250nm. Both compounds displayed moderate NIR fluorescence with fluorescence quantum yields of 4.4×10-6 and 6.0×10-6 for 1a and 1b, respectively. The NP-substituted porphyrin dimers 2a/2b have also been obtained by controlled oxidative coupling and cyclodehydrogenation, and they showed superimposed absorptions of the fused porphyrin dimer and the NP chromophore. The excited-state dynamics of all of these compounds have been studied by femtosecond transient absorption measurements, which revealed porphyrin dimer-like behaviour. These new chromophores also exhibited good nonlinear optical susceptibility with large two-photon absorption cross-sections in the NIR region due to extended π-conjugation. Time-dependent density functional theory calculations have been performed to aid our understanding of their electronic structures and absorption spectra.

  20. Consecutive thiophene-annulation approach to π-extended thienoacene-based organic semiconductors with [1]benzothieno[3,2-b][1]benzothiophene (BTBT) substructure.

    Science.gov (United States)

    Mori, Takamichi; Nishimura, Takeshi; Yamamoto, Tatsuya; Doi, Iori; Miyazaki, Eigo; Osaka, Itaru; Takimiya, Kazuo

    2013-09-18

    We describe a new synthetic route to the [1]benzothieno[3,2-b][1]benzothiophene (BTBT) substructure featuring two consecutive thiophene-annulation reactions from o-ethynyl-thioanisole substrates and arylsulfenyl chloride reagents that can be easily derived from arylthiols. The method is particularly suitable for the synthesis of unsymmetrical derivatives, e.g., [1]benzothieno[3,2-b]naphtho[2,3-b]thiophene, [1]benzothieno[3,2-b]anthra[2,3-b]thiophene, and naphtho[3,2-b]thieno[3,2-b]anthra[2,3-b]thiophene, a selenium-containing derivative, [1]benzothieno[3,2-b][1]benzoselenophene. It also allows us to access largely π-extended derivatives with two BTBT substructures, e.g., bis[1]benzothieno[2,3-d:2',3'-d']benzo[1,2-b:4,5-b']dithiophene and bis[1]benzothieno[2,3-d:2',3'-d']naphtho[2,3-b:6,7-b']dithiophene (BBTNDT). It should be emphasized that these new BTBT derivatives are otherwise difficult to be synthesized. In addition, since various substrates and reagents, o-ethynyl-thioanisoles and arylthiols, respectively, can be combined, the method can be regarded as a versatile tool for the development of thienoacene-based organic semiconductors in this class. Among the newly synthesized materials, highly π-extended BBTNDT afforded very high mobility (>5 cm(2) V(-1) s(-1)) in its vapor-deposited organic field-effect transistors (OFETs), which is among the highest for unsubstituted acene- or thienoacenes-based organic semiconductors. In fact, the structural analyses of BBTNDT both in the single crystal and thin-film state indicated that an interactive two-dimensional molecular array is realized in the solid state, which rationalize the higher carrier mobility in the BBTNDT-based OFETs.

  1. Palladium-Catalyzed, N-(2-Aminophenyl)acetamide-Assisted Ortho-Arylation of Substituted Benzamides: Application to the Synthesis of Urolithins B, M6, and M7.

    Science.gov (United States)

    Reddy, M Damoder; Blanton, Alexandra N; Watkins, E Blake

    2017-05-19

    Pd-catalyzed, selective, monoarylation of ortho-C-H bonds of various benzamides with aryl/heteroaryl iodides has been realized using N-(2-aminophenyl)acetamide (APA) as a new bidentate directing group for the first time. The reaction was tolerant of a wide range of functional groups, and a variety of biaryl amide derivatives were successfully prepared in good to moderate yield. The utilization of N-(2-aminophenyl)acetamide as a novel directing group, Mn(OAc) 2 as a co-oxidant (silver free reaction conditions), and absolute ortho-monoaryl selectivity are notable features of this reaction. In addition, the obtained monoarylated products could be further transformed into the bioactive natural products and human microflora metabolites of dietary ellagic acid derivatives, urolithin B, urolithin M6, and urolithin M7.

  2. Palladium-catalyzed meta-selective C-H bond activation with a nitrile-containing template: computational study on mechanism and origins of selectivity.

    Science.gov (United States)

    Yang, Yun-Fang; Cheng, Gui-Juan; Liu, Peng; Leow, Dasheng; Sun, Tian-Yu; Chen, Ping; Zhang, Xinhao; Yu, Jin-Quan; Wu, Yun-Dong; Houk, K N

    2014-01-08

    Density functional theory investigations have elucidated the mechanism and origins of meta-regioselectivity of Pd(II)-catalyzed C-H olefinations of toluene derivatives that employ a nitrile-containing template. The reaction proceeds through four major steps: C-H activation, alkene insertion, β-hydride elimination, and reductive elimination. The C-H activation step, which proceeds via a concerted metalation-deprotonation (CMD) pathway, is found to be the rate- and regioselectivity-determining step. For the crucial C-H activation, four possible active catalytic species-monomeric Pd(OAc)2, dimeric Pd2(OAc)4, heterodimeric PdAg(OAc)3, and trimeric Pd3(OAc)6-have been investigated. The computations indicated that the C-H activation with the nitrile-containing template occurs via a Pd-Ag heterodimeric transition state. The nitrile directing group coordinates with Ag while the Pd is placed adjacent to the meta-C-H bond in the transition state, leading to the observed high meta-selectivity. The Pd2(OAc)4 dimeric mechanism also leads to the meta-C-H activation product but with higher activation energies than the Pd-Ag heterodimeric mechanism. The Pd monomeric and trimeric mechanisms require much higher activation free energies and are predicted to give ortho products. Structural and distortion energy analysis of the transition states revealed significant effects of distortions of the template on mechanism and regioselectivity, which provided hints for further developments of new templates.

  3. Synthesis of 2-Substituted Furo[2,3-b]- and Furo[3,2-c]quinolines via Heterogeneous Palladium-catalyzed Heteroannulation

    Energy Technology Data Exchange (ETDEWEB)

    Park, Hee Jung [Korea Basic Science Institute, Seoul (Korea, Republic of); Yang, Ok-Kyung; Park, Young Chul; Yum, Eul Kgun [Chungnam National University, Daejon (Korea, Republic of)

    2016-06-15

    As a part of our continuing organometallic studies on diversification of nitrogen-containing biologically active heterocycles, we attempted to synthesize furo[2,3-b]- and furo[3,2-c]quinolines starting from o-halohydroxyquinolines and terminal alkynes with heterogeneous Pd(OAc)2 catalyst, which was supported by nanosized pore carbon ball. 2-substituted furo[2,3-b]quinolines and furo[3,2-c]quinolines were synthesized from the reaction of 3-iodoquinolin-2-ol and 3-iodoquinolin-4-ol, respectively, with diverse alkynes. The heteroannulation reaction proceeds with Sonogashira coupling followed by 5-endo-dig cyclization in good isolated yields under copper and ligand free conditions.

  4. γ‐ and δ-Lactams through Palladium-Catalyzed Intramolecular Allylic Alkylation: Enantioselective Synthesis, NMR Investigation, and DFT Rationalization

    DEFF Research Database (Denmark)

    Bantreil, Xavier; Prestat, Guillaume; Moreno, Aitor

    2011-01-01

    the cyclization reactions to take place in up to 94:6 enantiomeric ratio. A model Pd-allyl complex has been prepared and studied through NMR spectroscopic analysis, which provided insight into the processes responsible for the observed enantiomeric ratios. DFT studies were used to characterize the diastereomeric...

  5. Synthesis of 2-Substituted Furo[2,3-b]- and Furo[3,2-c]quinolines via Heterogeneous Palladium-catalyzed Heteroannulation

    International Nuclear Information System (INIS)

    Park, Hee Jung; Yang, Ok-Kyung; Park, Young Chul; Yum, Eul Kgun

    2016-01-01

    As a part of our continuing organometallic studies on diversification of nitrogen-containing biologically active heterocycles, we attempted to synthesize furo[2,3-b]- and furo[3,2-c]quinolines starting from o-halohydroxyquinolines and terminal alkynes with heterogeneous Pd(OAc)2 catalyst, which was supported by nanosized pore carbon ball. 2-substituted furo[2,3-b]quinolines and furo[3,2-c]quinolines were synthesized from the reaction of 3-iodoquinolin-2-ol and 3-iodoquinolin-4-ol, respectively, with diverse alkynes. The heteroannulation reaction proceeds with Sonogashira coupling followed by 5-endo-dig cyclization in good isolated yields under copper and ligand free conditions

  6. New Palladium-Catalyzed Domino Reaction with Intramolecular Ring Closure of an N-(2-Chloro-3-heteroaryl) arylamide: First Synthesis of Oxazolo[4,5-b] pyrazines

    DEFF Research Database (Denmark)

    Demmer, Charles S.; Hansen, Jacob C.; Kehler, Jan

    2014-01-01

    The synthesis of novel planar heterocycles is at the heart of basic research as such scaffolds constitute key building blocks in important diverse areas of research: drug discovery, material sciences, and pesticides. The well-known benzoxazole is often contained in drug candidates but tweaking its...... lipophilicity and target interaction points are often desired. In this respect, the oxazolo[4,5-b]pyrazine is an attractive heterocyclic scaffold as it possesses increased water solubility as well as two additional hydrogen bonding acceptors. We here report a new Pd(II)-catalyzed domino reaction comprising...... the first Pd(II)-assisted intramolecular cyclization of an N-(2-chloro-3-heteroaryl)arylamide and validate its value by application to the first synthesis of 2-substituted oxazolo[4,5-b]pyrazines. We demonstrate that a bidentate phosphorus ligand as well as the presence of an aromatic nitrogen atom...

  7. Palladium-Catalyzed Direct C-H Arylations of Dioxythiophenes Bearing Reactive Functional Groups: A Step-Economical Approach for Functional π-Conjugated Oligoarenes

    KAUST Repository

    Liu, Ching-Yuan

    2015-06-25

    A Pd-catalyzed and single-step C-H arylation of dioxythiophene derivates bearing unprotected reactive functional groups (-OH, -COOH, -N3) in a phosphine-free manner has been developed. Various dioxythiopene-based oligoarenes with extended π-conjugation are obtained with good yields (up to 90%). These oligoarenes display suitable optical properties (absorption and emission maxima, quantum yields) and contain reactive functional groups suitable for further conjugations with bioactive molecules. This new methodology is step economical (fewer synthetic steps), environmental friendly (no toxic metal-containing side-poducts) and the oligoarenes synthesized are potentially applicable for bio-labeling, bioimaging, and biosensing.

  8. Palladium-catalyzed aerobic regio- and stereo-selective olefination reactions of phenols and acrylates via direct dehydrogenative C(sp2)-O cross-coupling.

    Science.gov (United States)

    Wu, Yun-Bin; Xie, Dan; Zang, Zhong-Lin; Zhou, Cheng-He; Cai, Gui-Xin

    2018-04-26

    An efficient olefination protocol for the oxidative dehydrogenation of phenols and acrylates has been achieved using a palladium catalyst and O2 as the sole oxidant. This reaction exhibits high regio- and stereo-selectivity (E-isomers) with moderate to excellent isolated yields and a wide substrate scope (32 examples) including ethyl vinyl ketone and endofolliculina.

  9. Palladium-Catalyzed Formal Cross-Coupling of Diaryl Ethers with Amines: Slicing the 4-O-5 Linkage in Lignin Models.

    Science.gov (United States)

    Zeng, Huiying; Cao, Dawei; Qiu, Zihang; Li, Chao-Jun

    2018-03-26

    Lignin is the second most abundant organic matter on Earth, and is an underutilized renewable source for valuable aromatic chemicals. For future sustainable production of aromatic compounds, it is highly desirable to convert lignin into value-added platform chemicals instead of using fossil-based resources. Lignins are aromatic polymers linked by three types of ether bonds (α-O-4, β-O-4, and 4-O-5 linkages) and other C-C bonds. Among the ether bonds, the bond dissociation energy of the 4-O-5 linkage is the highest and the most challenging to cleave. To date, 4-O-5 ether linkage model compounds have been cleaved to obtain phenol, cyclohexane, cyclohexanone, and cyclohexanol. The first example of direct formal cross-coupling of diaryl ether 4-O-5 linkage models with amines is reported, in which dual C(Ar)-O bond cleavages form valuable nitrogen-containing derivatives. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Preparation of 5-acyl- and 5-aryl-substituted 1-(benzyloxy)pyrazoles via directed ortho-lithiation/transmetalation and palladium catalyzed cross- coupling

    DEFF Research Database (Denmark)

    Kristensen, Jesper Langgaard; Begtrup, M.; Vedsø, P.

    1998-01-01

    Palladium(0) catalyzed cross-coupling of 1-(benzyloxy)pyrazol-5-ylzinc halides 3a,b, prepared by transmetalation of 1-(benzyloxy)-5-lithiopyrazole (2), with acyl chlorides produced 5 acyl-1-(benzyloxy)pyrazoles 4a-d in high yields. Similar coupling of the pyrazol-5-ylzinc halide with amino-, hydr...

  11. Palladium-Catalyzed Direct C-H Arylations of Dioxythiophenes Bearing Reactive Functional Groups: A Step-Economical Approach for Functional π-Conjugated Oligoarenes

    KAUST Repository

    Liu, Ching-Yuan; Chong, Hui; Lin, Hsing-An; Yamashita, Yoshiro; Zheng, Bin; Huang, Kuo-Wei; Hashizume, Daisuke; Yu, Hsiao-hua

    2015-01-01

    A Pd-catalyzed and single-step C-H arylation of dioxythiophene derivates bearing unprotected reactive functional groups (-OH, -COOH, -N3) in a phosphine-free manner has been developed. Various dioxythiopene-based oligoarenes with extended π-conjugation are obtained with good yields (up to 90%). These oligoarenes display suitable optical properties (absorption and emission maxima, quantum yields) and contain reactive functional groups suitable for further conjugations with bioactive molecules. This new methodology is step economical (fewer synthetic steps), environmental friendly (no toxic metal-containing side-poducts) and the oligoarenes synthesized are potentially applicable for bio-labeling, bioimaging, and biosensing.

  12. Rhodium(III)-catalyzed [3+2] annulation of 5-aryl-2,3-dihydro-1H-pyrroles with internal alkynes through C(sp²)-H/alkene functionalization.

    Science.gov (United States)

    Zhou, Ming-Bo; Pi, Rui; Hu, Ming; Yang, Yuan; Song, Ren-Jie; Xia, Yuanzhi; Li, Jin-Heng

    2014-10-13

    This study describes a new rhodium(III)-catalyzed [3+2] annulation of 5-aryl-2,3-dihydro-1H-pyrroles with internal alkynes using a Cu(OAc)2 oxidant for building a spirocyclic ring system, which includes the functionalization of an aryl C(sp(2))-H bond and addition/protonolysis of an alkene C=C bond. This method is applicable to a wide range of 5-aryl-2,3-dihydro-1H-pyrroles and internal alkynes, and results in the assembly of the spiro[indene-1,2'-pyrrolidine] architectures in good yields with excellent regioselectivities. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Synthesis of novel chromeno-annulated cis-fused pyrano[3,4-c]benzopyran and naphtho pyran derivatives via domino aldol-type/hetero Diels-Alder reaction and their cytotoxicity evaluation.

    Science.gov (United States)

    Madda, Jyothi; Venkatesham, Akkaladevi; Naveen Kumar, Bejjanki; Nagaiah, Kommu; Sujitha, Pombala; Ganesh Kumar, C; Rao, Tadikamalla Prabhakar; Jagadeesh Babu, Nanubolu

    2014-09-15

    New chromeno-annulated cis-fused pyrano[3,4-c]benzopyran and naphtho pyran derivatives have been synthesized by domino aldol-type reaction/hetero Diels-Alder reaction generated from o-quinone methide in situ from 7-O-prenyl derivatives of 8-formyl-2,3-disubstituted chromenones with resorcinols/naphthols in the presence of 20 mol% ethylenediamine diacetate (EDDA), triethylamine (2 mL) as co-catalyst in CH3CN under reflux conditions in good yields. The structures were established based on spectroscopic data, and further confirmed by X-ray diffraction analysis. The results showed that compounds 4h and 4j exhibited very potent cytotoxicity against human cervical cancer cell line (HeLa). Compound 4h displayed good inhibitory activity against both breast cancer cell lines, MDA-MB-231 and MCF-7. Further, the compound 4i exhibited good cytotoxicity against only MDA-MB-231, and compound 4j showed promising activity against human lung cancer cell line, A549 with IC50 value of 2.53±0.07 μM, which was comparable to the standard doxorubicin (IC50=1.21±0.1 μM). Copyright © 2014 Elsevier Ltd. All rights reserved.

  14. N -annulated perylene as an efficient electron donor for porphyrin-based dyes: Enhanced light-harvesting ability and high-efficiency Co(II/III)-based dye-sensitized solar cells

    KAUST Repository

    Luo, Jie

    2014-01-08

    Porphyrin-based dyes recently have become good candidates for dye-sensitized solar cells (DSCs). However, the bottleneck is how to further improve their light-harvesting ability. In this work, N-annulated perylene (NP) was used to functionalize the Zn-porphyrin, and four "push-pull"-type NP-substituted and fused porphyrin dyes with intense absorption in the visible and even in the near-infrared (NIR) region were synthesized. Co(II/III)-based DSC device characterizations revealed that dyes WW-5 and WW-6, in which an ethynylene spacer is incorporated between the NP and porphyrin core, showed pantochromatic photon-to-current conversion efficiency action spectra in the visible and NIR region, with a further red-shift of about 90 and 60 nm, respectively, compared to the benchmark molecule YD2-o-C8. As a result, the short-circuit current density was largely increased, and the devices displayed power conversion efficiencies as high as 10.3% and 10.5%, respectively, which is comparable to that of the YD2-o-C8 cell (η = 10.5%) under the same conditions. On the other hand, the dye WW-3 in which the NP unit is directly attached to the porphyrin core showed a moderate power conversion efficiency (η = 5.6%) due to the inefficient π-conjugation, and the NP-fused dye WW-4 exhibited even poorer performance due to its low-lying LUMO energy level and nondisjointed HOMO/LUMO profile. Our detailed physical measurements (optical and electrochemical), density functional theory calculations, and photovoltaic characterizations disclosed that the energy level alignment, the molecular orbital profile, and dye aggregation all played very important roles on the interface electron transfer and charge recombination kinetics. © 2013 American Chemical Society.

  15. Journal of Chemical Sciences | Indian Academy of Sciences

    Indian Academy of Sciences (India)

    Carbazole-based sensitizers for potential application to dye sensitized solar cells ... Iodobenzene diacetate-mediated isomerization of pyrazolyl chalcones and their .... of oximes to their corresponding carbonyl compounds in aqueous medium .... substituted with a phenyl group, the energy barriers for 5-exo-dig cyclization or ...

  16. Synthesis of 4-substituted tetrahydropyridines by cross-coupling of enol phosphates

    DEFF Research Database (Denmark)

    Larsen, U.S.; Martiny, L.; Begtrup, M.

    2005-01-01

    Enol phosphates, synthesized from 4-piperidone, react by palladium catalyzed cross-coupling with arylboronic acids and by iron and palladium catalyzed cross-coupling with Grignard reagents to give 4-substituted tetrahydropyridines. (c) 2005 Elsevier Ltd. All rights reserved....

  17. Enantioselective solvent-free Robinson annulation reactions

    Indian Academy of Sciences (India)

    Unknown

    solvents to effect an asymmetric synthesis is an important step forward towards ... In continuation of our preliminary communication 2, we wish to ..... formation of chiral enamine 74 from the reaction of S-proline with pro-R carbonyl group.

  18. Synthesis of 2-Amino-3-hydroxy-3H-indoles via Palladium-Catalyzed One-Pot Reaction of Isonitriles, Oxygen, and N-Tosylhydrazones Derived from 2-Acylanilines.

    Science.gov (United States)

    Chu, Haoke; Dai, Qiang; Jiang, Yan; Cheng, Jiang

    2017-08-04

    A cyanide-free one-pot procedure was developed to access 2-amino-3-hydroxy-3H-indoles, which involved: (1) in situ formation of ketenimines by the reaction of N'-(1-(2-aminophenyl)ethylidene)-p-tosylhydrazones with isonitriles; (2) the intramolecular nucleophilic attack of ketenimines by the amino in phenyl furnishing the ring closure leading to 2-aminoindoles; (3) the oxidation of 2-aminoindoles by O 2 leading to 2-amino-3-hydroxy-3H-indoles. This strategy represents not only a key compliment to the sporadic synthetic methods toward 2-amino-3-hydroxy-3H-indoles but also progress in N-tosylhydrazone, isonitrile, and ketenimine chemistry.

  19. Palladium-Catalyzed Asymmetric Conjugate Addition of Arylboronic Acids to Five-, Six-, and Seven-Membered β-Substituted Cyclic Enones: Enantioselective Construction of All-Carbon Quaternary Stereocenters

    KAUST Repository

    Kikushima, Kotaro

    2011-05-11

    The first enantioselective Pd-catalyzed construction of all-carbon quaternary stereocenters via 1,4-addition of arylboronic acids to β-substituted cyclic enones is reported. Reaction of a wide range of arylboronic acids and cyclic enones using a catalyst prepared from Pd(OCOCF(3))(2) and a chiral pyridinooxazoline ligand yields enantioenriched products bearing benzylic stereocenters. Notably, this transformation is tolerant to air and moisture, providing a practical and operationally simple method of synthesizing enantioenriched all-carbon quaternary stereocenters.

  20. SUBSTITUENT EFFECTS OF LIGANDS ON ASYMMETRIC INDUCTION IN A PROTOTYPICAL PALLADIUM-CATALYZED ALLYLATION REACTION: MAKING BOTH ENANTIOMERS OF A PRODUCT IN HIGH OPTICAL PURITY USING THE SAME SOURCE OF CHIRALITY. (R826120)

    Science.gov (United States)

    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

  1. Two Palladium-Catalyzed Domino Reactions from One Set of Substrates/Reagents: Efficient Synthesis of Substituted Indenes and cis-Stilbenoid Hydrocarbons from the Same Internal Alkynes and Hindered Grignard Reagents

    Science.gov (United States)

    Dong, Cheng-Guo; Yeung, Pik; Hu, Qiao-Sheng

    2008-01-01

    Two types of domino reactions from the same internal alkynes and hindered Grignard reagents based on carbopalladation, Pd-catalyzed cross-coupling reaction and C-H activation strategy are described. The realization of these domino reactions relied on the control of the use of the ligand and the reaction temperature. Our study provides an efficient access to useful polysubstituted indenes and cis-substituted stilbenes, and may offer new means to the development of tandem/domino reactions in a more efficient way. PMID:17217305

  2. Palladium-Catalyzed Asymmetric Conjugate Addition of Arylboronic Acids to Five-, Six-, and Seven-Membered β-Substituted Cyclic Enones: Enantioselective Construction of All-Carbon Quaternary Stereocenters

    KAUST Repository

    Kikushima, Kotaro; Holder, Jeffrey C.; Gatti, Michele; Stoltz, Brian M.

    2011-01-01

    The first enantioselective Pd-catalyzed construction of all-carbon quaternary stereocenters via 1,4-addition of arylboronic acids to β-substituted cyclic enones is reported. Reaction of a wide range of arylboronic acids and cyclic enones using a

  3. Deconstructing selectivity in the gold-promoted cyclization of alkynyl benzothioamides to six-membered mesoionic carbene or acyclic carbene complexes

    KAUST Repository

    Vummaleti, Sai V. C.; Falivene, Laura; Poater, Albert; Cavallo, Luigi

    2014-01-01

    We demonstrate that the experimentally observed switch in selectivity from 5-exo-dig to 6-endo-dig cyclization of an alkynyl substrate, promoted by Au I and AuIII complexes, is connected to a switch from thermodynamic to kinetic reaction control. The AuIII center pushes alkyne coordination toward a single Au-C(alkyne) σ-bond, conferring carbocationic character (and reactivity) to the distal alkyne C atom. © 2014 American Chemical Society.

  4. Gold(I-catalyzed domino cyclization for the synthesis of polyaromatic heterocycles

    Directory of Open Access Journals (Sweden)

    Mathieu Morin

    2013-11-01

    Full Text Available Gold(I complexes have emerged as powerful and useful catalysts for the formation of new C–C, C–O and C–N bonds. Taking advantage of the specificity of [IPrAuNCMe][SbF6] complexes to favor the 5-exo-dig cyclization over the 6-endo-dig pathway, we report a high yielding and efficient method to generate substituted polyaromatic heterocycles under remarkably mild reaction conditions.

  5. Deconstructing selectivity in the gold-promoted cyclization of alkynyl benzothioamides to six-membered mesoionic carbene or acyclic carbene complexes

    KAUST Repository

    Vummaleti, Sai V. C.

    2014-05-02

    We demonstrate that the experimentally observed switch in selectivity from 5-exo-dig to 6-endo-dig cyclization of an alkynyl substrate, promoted by Au I and AuIII complexes, is connected to a switch from thermodynamic to kinetic reaction control. The AuIII center pushes alkyne coordination toward a single Au-C(alkyne) σ-bond, conferring carbocationic character (and reactivity) to the distal alkyne C atom. © 2014 American Chemical Society.

  6. N-(m-[125I]iodophenyl)maleimide: an agent for high yield radiolabeling of antibodies

    International Nuclear Information System (INIS)

    Khawli, L.A.; Van den Abbeele, A.D.; Kassis, A.I.

    1992-01-01

    In an effort to radiolabel antibodies, N-(m-[ 125 I]iodophenyl)maleimide (m-[ 125 I]IPM) was prepared by the demetallation of an N-[m-tri-(n-butyl)stannylphenyl]maleimide intermediate. The unlabeled intermediate was synthesized in ≥ 75% yield using a palladium catalyzed reaction of hexabutylditin with m-bromoaniline, followed by reaction with maleic anhydride and ring annulation. All products were confirmed by NMR and elemental analysis. Labeling with 125 I was carried out in a biphasic mixture containing chloramine-T (radiochemical yield ≥ 70%). Rabbit IgG modified with the heterobifunctional crosslinking agent N-succinimidyl-3-(2-pyridyldithio)propionate (SPDP) and bovine serum albumin were conjugated with m-[ 125 I]IPM (yield: 40 and 80%, respectively). In addition, m-[ 125 I]IPM was conjugated to rabbit IgG subunits (HL) in 70% yield. The in vitro stability of the radiolabeled proteins in serum showed < 1% deiodination over 24h. (author)

  7. Ebola Virus Inactivation by Detergents Is Annulled in Serum

    NARCIS (Netherlands)

    van Kampen, Jeroen J. A.; Tintu, Andrei; Russcher, Henk; Fraaij, Pieter L. A.; Reusken, Chantal B. E. M.; Rijken, Mikel; van Hellemond, Jaap J.; van Genderen, Perry J. J.; Koelewijn, Rob; de Jong, Menno D.; Haddock, Elaine; Fischer, Robert J.; Munster, Vincent J.; Koopmans, Marion P. G.

    2017-01-01

    Treatment of blood samples from hemorrhagic fever virus (HFV)-infected patients with 0.1% detergents has been recommended for virus inactivation and subsequent safe laboratory testing. However, data on virus inactivation by this procedure are lacking. Here we show the effect of this procedure on

  8. Lattelecom "deal of century" on verge of annulment

    Index Scriptorium Estoniae

    2007-01-01

    Läti majandusministri kohusetäitja Gaidis Berzins teatas Lattelecomi juhatuse esimehele Nils Melngailisele, et tema töölepingut ei pikendata. Asjaolu pidurdab Lattelecomi erastamist investeerimisfirmale Blackstone Group ja Lattelecomi töötajatele

  9. Steelhead Kelt Reconditioning and Reproductive Success, 2008 Annul Report.

    Energy Technology Data Exchange (ETDEWEB)

    Hatch, Douglas R. [Columbia River Inter-Tribal Fish Commission

    2009-04-02

    Iteroparity, the ability to repeat spawn, is a natural life history strategy that is expressed by some species from the family Salmonidae. Current rates of observed steelhead Oncorhynchus mykiss iteroparity rates in the Columbia River Basin are severely depressed due to anthropogenic development which includes operation of the hydropower system and other habitat degradations. Artificial reconditioning, which is the process of culturing post-spawned fish (kelts) in a captive environment until they are able to reinitiate feeding, growth, and redevelop mature gonads, is evaluated in this study as method to restore depressed steelhead populations. To test the efficacy of steelhead kelt reconditioning as a management and recovery tool different scenarios were investigated ranging from very low intensity (collect and transport fish) to high intensity (collect and feed fish in captivity until rematuration). Examinations of gamete and progeny viability were performed for first-time spawners and reconditioned kelt steelhead. We have continued to examine reproductive success of reconditioned kelt steelhead in Omak Creek using microsatellite loci to perform parentage analysis on juvenile O. mykiss . The groundwork has also begun on developing a genetic analysis of the Yakima subbasin in order to determine steelhead kelt contribution by utilizing parentage analysis on a larger scale. A research and study plan has been developed cooperatively with the University of Idaho to determine the feasibility of steelhead kelt reconditioning program in the Snake River Basin. Analysis of management scenarios indicated that while no-term and short-term reconditioned kelts continue to perform well outmigrating to the ocean but returns from these groups have been low ranging from 0-12% during 2002-2008. Survival (56%) of fish in the long-term treatment in 2008 was the highest we have observed in this project. Analyzing the three different management scenarios within the Yakima River subbasin we determined that long-term reconditioning contributed the highest numbers of fish to the spawning run, and short-term reconditioning overall was the best of the transport releases to the ocean. However contributions to the spawning run by no-term or short-term groups was low in all years. This is the second successful year of kelt gamete and progeny analysis. Initial limited results suggest that reconditioned kelts may have shown limited improvement in both egg quantity and/or quality. There is further evidence to support the successful spawning of steelhead kelts in the wild at Omak Creek. Yakima kelts have been successfully identified to stream origin using genotypes.

  10. Rapid synthesis of polyprenylated acylphloroglucinol analogs via dearomative conjunctive allylic annulation.

    Science.gov (United States)

    Grenning, Alexander J; Boyce, Jonathan H; Porco, John A

    2014-08-20

    Polyprenylated acylphloroglucinols (PPAPs) are structurally complex natural products with promising biological activities. Herein, we present a biosynthesis-inspired, diversity-oriented synthesis approach for rapid construction of PPAP analogs via double decarboxylative allylation (DcA) of acylphloroglucinol scaffolds to access allyl-desoxyhumulones followed by dearomative conjunctive allylic alkylation (DCAA).

  11. Base-catalyzed efficient tandem [3 + 3] and [3 + 2 + 1] annulation-aerobic oxidative benzannulations.

    Science.gov (United States)

    Diallo, Aboubacar; Zhao, Yu-Long; Wang, He; Li, Sha-Sha; Ren, Chuan-Qing; Liu, Qun

    2012-11-16

    An efficient synthesis of substituted benzenes via a base-catalyzed [3 + 3] aerobic oxidative aromatization of α,β-unsaturated carbonyl compounds with dimethyl glutaconate was reported. All the reactions were carried out under mild, metal-free conditions to afford the products in high to excellent yields with molecular oxygen as the sole oxidant and water as the sole byproduct. Furthermore, a more convenient tandem [3 + 2 + 1] aerobic oxidative aromatization reaction was developed through the in situ generation of the α,β-unsaturated carbonyl compounds from aldehydes and ketones.

  12. Aspects of No Endorsement of Annulment Provided Without Granting the Union Stable

    Directory of Open Access Journals (Sweden)

    Juliana Franco Fulgencio Fonseca

    2015-12-01

    Full Text Available Given the importance of the endorsement in corporate economic activities, the study has the scope to analysis of change brought about by the Civil Code of 2002, which caused expressed spousal authorization requirement to validate guarantee provided by the other, except for cases of separation regime total assets. Innovation led an intense doctrinal discussion, given that the norm has brought significant changes to the guarantor and institute such a levy was not provided for in the Civil Code of 1916. It is a critical analysis of art. 1647, III of the Civil Code on the context of the general theory of debt securities and its principles, calling for the dynamism and simplicity of credit flowing. Clarify to the approval of the consequences provided without granting the marriage scope and stable, as well as the applicability or inapplicability of such a charge against the securities. The study underpins that, besides being unnecessary to grant the guarantee provided by the cohabitant in a stable relationship, even if it were necessary, would not occur invalidity of endorsement (as stipulated by the Civil Code of 2002, but the ineffectiveness have no effect before one who did not attend the act.

  13. Design and synthesis of novel bis-annulated caged polycycles via ring-closing metathesis: pushpakenediol

    Directory of Open Access Journals (Sweden)

    Sambasivarao Kotha

    2014-11-01

    Full Text Available Intricate caged molecular frameworks are assembled by an atom economical process via a Diels–Alder (DA reaction, a Claisen rearrangement, a ring-closing metathesis (RCM and an alkenyl Grignard addition. The introduction of olefinic moieties in the pentacycloundecane (PCUD framework at appropriate positions followed by RCM led to the formation of novel heptacyclic cage systems.

  14. Annulated heterocyclic bioisosteres of norarecoline. Synthesis and molecular pharmacology at five recombinant human muscarinic acetylcholine receptors

    DEFF Research Database (Denmark)

    Bräuner-Osborne, Hans; Ebert, B; Brann, M R

    1995-01-01

    = 0.011 microM), and 4d (IC50 = 0.0008 microM). Pharmacological effects (EC50 or Ki values) and intrinsic activities (per cent of maximal carbachol responses) were determined using five recombinant human mAChRs (m1-m5) and the functional assay, receptor selection and amplification technology (R...... inhibitors of the binding of tritiated quinuclidinyl benzilate (QNB), pirenzepine (PZ), and oxotremorine-M (Oxo-M) to tissue membrane preparations. In the [3H]-Oxo-M binding assay, receptor affinities in the low nanomolar range were measured for 4a (IC50 = 0.010 microM), 4b (IC50 = 0.003 microM), 4c (IC50...

  15. Spiro annulation of cage polycycles via Grignard reaction and ring-closing metathesis as key steps

    Directory of Open Access Journals (Sweden)

    Sambasivarao Kotha

    2015-08-01

    Full Text Available A simple synthetic strategy to C2-symmetric bis-spiro-pyrano cage compound 7 involving ring-closing metathesis is reported. The hexacyclic dione 10 was prepared from simple and readily available starting materials such as 1,4-naphthoquinone and cyclopentadiene. The synthesis of an unprecedented octacyclic cage compound through intramolecular Diels–Alder (DA reaction as a key step is described. The structures of three new cage compounds 7, 12 and 18 were confirmed by single crystal X-ray diffraction studies.

  16. Benzo[b]fluorenes via indanone dianion annulation: a short synthesis of prekinamycin.

    Science.gov (United States)

    Birman, Vladimir B; Zhao, Zhufeng; Guo, Lei

    2007-03-29

    [structure: see text]. A rapid construction of benzo[b]fluorenones via reaction of 1-indanone dianions with phthalate diesters is described. Its utility is illustrated with a concise synthesis of prekinamycin.

  17. Synthesis, Anticonvulsant, Sedative and Anxiolytic Activities of Novel Annulated Pyrrolo[1,4]benzodiazepines

    Directory of Open Access Journals (Sweden)

    Kumaraswamy Sorra

    2014-09-01

    Full Text Available Four new pentacyclic benzodiazepine derivatives (PBDTs 13–16 were synthesized by conventional thermal heating and microwave-assisted intramolecular cyclocondensation. Their anticonvulsant, sedative and anxiolytic activities were evaluated by drug-induced convulsion models, a pentobarbital-induced hypnotic model and an elevated plus maze in mice. PBDT 13, a triazolopyrrolo[2,1-c][1,4]benzodiazepin-8-one fused with a thiadiazolone ring, exhibited the best anticonvulsant, sedative and anxiolytic effects in our tests. There was no significant difference in potency between PBDT 13 and diazepam, and we proposed that the action mechanism of PBDT 13 could be similar to that of diazepam via benzodiazepine receptors.

  18. Aspects of No Endorsement of Annulment Provided Without Granting the Union Stable

    OpenAIRE

    Juliana Franco Fulgencio Fonseca

    2015-01-01

    Given the importance of the endorsement in corporate economic activities, the study has the scope to analysis of change brought about by the Civil Code of 2002, which caused expressed spousal authorization requirement to validate guarantee provided by the other, except for cases of separation regime total assets. Innovation led an intense doctrinal discussion, given that the norm has brought significant changes to the guarantor and institute such a levy was not provided for in the Civil Code ...

  19. Regioselective syntheses of 1,2-benzothiazines by rhodium-catalyzed annulation reactions.

    Science.gov (United States)

    Cheng, Ying; Bolm, Carsten

    2015-10-12

    Rhodium-catalyzed directed carbene insertions into aromatic CH bonds of S-aryl sulfoximines lead to intermediates, which upon dehydration provide 1,2-benzothiazines in excellent yields. The domino-type process is regioselective and shows a high functional-group tolerance. It is scalable, and the only by-products are dinitrogen and water. Three illustrative transformations underscore the synthetic value of the products. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. A dual Lewis base activation strategy for enantioselective carbene-catalyzed annulations.

    Science.gov (United States)

    Izquierdo, Javier; Orue, Ane; Scheidt, Karl A

    2013-07-24

    A dual activation strategy integrating N-heterocyclic carbene (NHC) catalysis and a second Lewis base has been developed. NHC-bound homoenolate equivalents derived from α,β-unsaturated aldehydes combine with transient reactive o-quinone methides in an enantioselective formal [4 + 3] fashion to access 2-benzoxopinones. The overall approach provides a general blueprint for the integration of carbene catalysis with additional Lewis base activation modes.

  1. An intramolecular inverse electron demand Diels–Alder approach to annulated α-carbolines

    Directory of Open Access Journals (Sweden)

    Zhiyuan Ma

    2012-06-01

    Full Text Available Intramolecular inverse electron demand cycloadditions of isatin-derived 1,2,4-triazines with acetylenic dienophiles tethered by amidations or transesterifications proceed in excellent yields to produce lactam- or lactone-fused α-carbolines. Beginning with various isatins and alkynyl dienophiles, a pilot-scale library of eighty-eight α-carbolines was prepared by using this robust methodology for biological evaluation.

  2. Rationalization of the selectivity between 1,3- and 1,2-migration: a DFT study on gold(i)-catalyzed propargylic ester rearrangement.

    Science.gov (United States)

    Jiang, Jingxing; Liu, Yan; Hou, Cheng; Li, Yinwu; Luan, Zihong; Zhao, Cunyuan; Ke, Zhuofeng

    2016-04-14

    Gold catalyzed rearrangement of propargylic esters can undergo 1,3-acyloxy migration to form allenes, or undergo 1,2-acyloxy migration to access gold-carbenoids. The variation in migration leads to different reactivities and diverse cascade transformations. The effect of terminal substituents is very important for the rearrangement. However, it remains ambiguous how terminal substituents govern the selectivity of the rearrangement. This study presents a theoretical model based on the resonance structure of gold activated propargylic ester complexes to rationalize the rearrangement selectivity. Substrates with a major resonance contributor A prefer 5-exo-dig cyclization (1,2-migration), while those with a major resonance contributor B prefer 6-endo-dig cyclization (1,3-migration). This concise model would be helpful in understanding and tuning the selectivity of the metal catalyzed rearrangement of propargylic esters.

  3. Selectivity switch in the synthesis of vinylgold(I) intermediates

    KAUST Repository

    Hashmi, A. Stephen K

    2011-11-28

    An unexpected regioselectivity reversal was observed in the synthesis of vinylgold(I) complexes from propargyl carboxamides. The use of [Au(IPr)(OH)] affords preferentially vinylgold(I) complexes resulting from a 5-exo-dig cyclization, whereas the use [Au(IPr)]+ species, generated in situ starting from [Au(IPr)(Cl)] and AgOTf, leads to vinylgold(I) complexes which form via a 6-endo-dig cyclization, This unexpected "selectivity switch" for this cyclization led us to propose two different reaction pathways enabling the formation of the two different products. One mechanism involves the [Au(IPr)]+ species with "classical" I activation of the alkyne framework of the carboxamides, and the second represents an "unusual" use of the basic Brønsted character of [Au(IPr)(OH)]. Mechanistic and DFT studies support the mechanistic hypotheses. © 2011 American Chemical Society.

  4. Selectivity switch in the synthesis of vinylgold(I) intermediates

    KAUST Repository

    Hashmi, A. Stephen K; Schuster, Andreas M.; Gaillard, Sylvain; Cavallo, Luigi; Poater, Albert; Nolan, Steven P.

    2011-01-01

    An unexpected regioselectivity reversal was observed in the synthesis of vinylgold(I) complexes from propargyl carboxamides. The use of [Au(IPr)(OH)] affords preferentially vinylgold(I) complexes resulting from a 5-exo-dig cyclization, whereas the use [Au(IPr)]+ species, generated in situ starting from [Au(IPr)(Cl)] and AgOTf, leads to vinylgold(I) complexes which form via a 6-endo-dig cyclization, This unexpected "selectivity switch" for this cyclization led us to propose two different reaction pathways enabling the formation of the two different products. One mechanism involves the [Au(IPr)]+ species with "classical" I activation of the alkyne framework of the carboxamides, and the second represents an "unusual" use of the basic Brønsted character of [Au(IPr)(OH)]. Mechanistic and DFT studies support the mechanistic hypotheses. © 2011 American Chemical Society.

  5. Chameleonic reactivity of vicinal diazonium salt of acetylenyl-9,10-anthraquinones: synthetic application toward two heterocyclic targets.

    Science.gov (United States)

    Stepanov, A A; Gornostaev, L M; Vasilevsky, S F; Arnold, E V; Mamatyuk, V I; Fadeev, D S; Gold, B; Alabugin, I V

    2011-11-04

    The nature of products in the diazotization of 1-amino-2-acetylenyl-9,10-anthraquinones strongly depends on the nature of substituents at both the alkyne and at the anthraquinone core. Donor substitution (NHAr, OH) at the fourth position stabilizes the diazonium salt at C1, decelerating electrophilic cyclization at the arylethynyl substituent at C2. This effect allows the replacement of the diazonium with azide group and subsequent closure into isoxazole ring with preservation of the alkyne. In contrast, electrophilic 5-exo-dig cyclizations to condensed pyrazoles is observed for the combination of donor substituents at the aryl alkyne moiety and an OAc substituent at C4. The latter process provides a new synthetic route to 3-ethynyl-[1,9-cd]isoxazol-6-ones that are difficult to access otherwise. DFT calculations suggest that donor substituents have only a minor effect on alkyne and diazonium polarization in the reactant but provide specific transition state stabilization by stabilizing the incipient vinyl cation. This analysis provides the first computational data on electrophilic 5-exo-dig cyclization in its parent form and the nucleophile-promoted version. This cyclization is a relatively fast but endothermic process that is rendered thermodynamically feasible by the enol-keto tautomerization with concomitant aromatization in the five-membered heteroaromatic ring. Computations suggest that the importance of nucleophilic assistance in the transition state for a relatively weak nucleophile such as water is minor because the energy gain due to the Lewis base coordination to the carbocationic center is more than compensated for by the unfavorable entropic term for the bimolecular proces.

  6. Synthesis of Rhodamines from Fluoresceins Using Pd-Catalyzed C–N Cross-Coupling

    Science.gov (United States)

    2011-01-01

    A unified, convenient, and efficient strategy for the preparation of rhodamines and N,N′-diacylated rhodamines has been developed. Fluorescein ditriflates were found to undergo palladium-catalyzed C–N cross-coupling with amines, amides, carbamates, and other nitrogen nucleophiles to provide direct access to known and novel rhodamine derivatives, including fluorescent dyes, quenchers, and latent fluorophores. PMID:22091952

  7. Effects of oxygen and catalyst on tetraphenylborate decomposition rate

    International Nuclear Information System (INIS)

    Walker, D.D.

    1999-01-01

    Previous studies indicate that palladium catalyzes rapid decomposition of alkaline tetraphenylborate slurries. Oxygen inhibits the reaction at low temperature (25 C), presumably by preventing activation of the catalyst. The present study investigated oxygen's inhibiting effectiveness at higher temperature (45 C) and catalyst concentrations

  8. Total Synthesis of Adunctin B.

    Science.gov (United States)

    Dethe, Dattatraya H; Dherange, Balu D

    2018-03-16

    Total synthesis of (±)-adunctin B, a natural product isolated from Piper aduncum (Piperaceae), has been achieved using two different strategies, in seven and three steps. The efficient approach features highly atom economical and diastereoselective Friedel-Crafts acylation, alkylation reaction and palladium catalyzed Wacker type oxidative cyclization.

  9. Tandem electrophilic cyclization-[3+2] cycloaddition-rearrangement reactions of 2-alkynylbenzaldoxime, DMAD, and Br2.

    Science.gov (United States)

    Ding, Qiuping; Wang, Zhiyong; Wu, Jie

    2009-01-16

    Tandem electrophilic cyclization-[3+2] cycloaddition-rearrangement reactions of 2-alkynylbenzaldoximes, DMAD, and bromine are described, which afford the unexpected isoquinoline-based azomethine ylides in good to excellent yields. The products could be further elaborated via palladium-catalyzed cross-coupling reactions to generate highly functionalized isoquinoline-based stable azomethine ylides.

  10. (2E-3-(3-Methoxy-1-phenyl-1H-pyrazol-4-yl-2-propenal

    Directory of Open Access Journals (Sweden)

    Algirdas Šačkus

    2009-12-01

    Full Text Available The palladium-catalyzed reaction of 4-bromo-3-methoxy-1-phenyl-1H-pyrazole with acrolein diethyl acetal gives the title compound in good yield. Detailed spectroscopic data (1H NMR, 13C NMR, 15N NMR, IR, MS are presented.

  11. C3 Epimerization of Glucose, via Regioselective Oxidation and Reduction

    NARCIS (Netherlands)

    Jumde, Varsha R.; Eisink, Niek N. H. M.; Witte, Martin D.; Minnaard, Adriaan J.

    2016-01-01

    Palladium-catalyzed oxidation can single out the secondary hydroxyl group at C3 in glucose, circumventing the more readily accessible hydroxyl at C6 and the more reactive anomeric hydroxyl. Oxidation followed by reduction results in either allose or allitol, each a rare sugar that is important in

  12. Efficient and Simple Synthesis of 6-Aryl-1,4-dimethyl-9H-carbazoles

    Directory of Open Access Journals (Sweden)

    Sylvain Rault

    2008-06-01

    Full Text Available A synthetic method for the preparation of 6-aryl-1,4-dimethyl-9H-carbazoles involving a palladium catalyzed coupling reaction of 1,4-dimethyl-9H-carbazole-6-boronic acids and (heteroaryl halides is described.

  13. Synthesis of (±)-amathaspiramide F and discovery of an unusual stereocontrolling element for the [2,3]-Stevens rearrangement.

    Science.gov (United States)

    Soheili, Arash; Tambar, Uttam K

    2013-10-04

    A formal total synthesis of (±)-amathaspiramide F through a tandem palladium-catalyzed allylic amination/[2,3]-Stevens rearrangement is reported. The unexpected diastereoselectivity of the [2,3]-Stevens rearrangement was controlled by the substitution patterns of an aromatic ring. This discovery represents a new stereocontrolling element for [2,3]-sigmatropic rearrangements in complex molecular settings.

  14. On the Nature of the Intermediates and the Role of Chloride Ions in Pd-Catalyzed Allylic Alkylations: Added Insight from Density Functional Theory

    DEFF Research Database (Denmark)

    Fristrup, Peter; Ahlquist, Mårten Sten Gösta; Tanner, David Ackland

    2008-01-01

    The reactivity of intermediates in palladium-catalyzed allylic alkylation was investigated using DFT (B3LYP) calculations including a PB-SCRF solvation model. In the presence of both phosphine and chloride ligands, the allyl intermediate is in equilibrium between a cationic eta(3)-allylPd complex...

  15. Fulltext PDF

    Indian Academy of Sciences (India)

    Konstantin Novoselov, University of Manchester, Manchester, United Kingdom. Chemistry. “for palladium-catalyzed cross couplings in organic synthesis” to. Richard F Heck, University of Delaware, USA;. Ei-ichi Negishi, Purdue University, West Lafayette, IN, USA;. Akira Suzuki, Hokkaido University, Sapporo, Japan.

  16. Microwave-Enhanced Cross-Coupling Reactions Involving Alkynyltrifluoroborates with Aryl Bromides

    Directory of Open Access Journals (Sweden)

    George W. Kabalka

    2013-01-01

    Full Text Available Palladium-catalyzed alkynylation has emerged as one of the most reliable methods for the synthesis of alkynes which are often used in natural product syntheses and material science. An efficient method for coupling alkynyltrifluoroborates with various aryl bromides in the presence of a palladium catalyst has been developed using microwave irradiation. The microwave reactions are rapid and efficient.

  17. Journal of Chemical Sciences | Indian Academy of Sciences

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 127; Issue 5. Application of quinoxaline based diimidazolium salt in palladium catalyzed cross-coupling reactions. Mujahuddin M Siddiqui Mohammed Waheed Sajad A Bhat Maravanji S Balakrishna. Regular Articles Volume 127 Issue 5 May 2015 pp 879-884 ...

  18. supp12a.doc

    Indian Academy of Sciences (India)

    for. Application of quinoxaline based diimidazolium salt in palladium catalyzed cross-coupling reactions. Mujahuddin M. Siddiqui, Mohammed Waheed, Sajad A. Bhat and Maravanji S. Balakrishna*. Organophosphorus and Homogenous catalysis laboratory, Department of Chemistry, Indian Institute of Technology Bombay, ...

  19. Oxidative Heck Reaction as a Tool for Para-selective Olefination of Aniline: A DFT Supported Mechanism.

    Science.gov (United States)

    Moghaddam, Firouz Matloubi; Pourkaveh, Raheleh; Karimi, Ashkan

    2017-10-06

    This study describes the first para-selective palladium-catalyzed alkenylation of tertiary amines. This regioselective C-H activation was conducted without any chelation moieties. A series of olefins were reacted under mild reaction conditions at 60 °C, and the corresponding products were obtained in good yields with high selectivity.

  20. Palladium(II)-catalyzed ortho-olefination of arenes applying sulfoxides as remote directing groups.

    Science.gov (United States)

    Wang, Binjie; Shen, Chuang; Yao, Jinzhong; Yin, Hong; Zhang, Yuhong

    2014-01-03

    A novel palladium-catalyzed ortho-C(sp(2))-H olefination protocol has been developed by the use of sulfoxide as the directing group. Importantly, relatively remote coordination can be accessed to achieve the ortho olefination of benzyl, 2-arylethyl, and 3-arylpropenyl sulfoxide substrates, and the olefinated sulfoxide can be easily transformed to other functionalities.

  1. Nickel(0)-catalyzed enantioselective annulations of alkynes and arylenoates enabled by a chiral NHC ligand: efficient access to cyclopentenones.

    Science.gov (United States)

    Ahlin, Joachim S E; Donets, Pavel A; Cramer, Nicolai

    2014-11-24

    Cyclopentenones are versatile structural motifs of natural products as well as reactive synthetic intermediates. The nickel-catalyzed reductive [3+2] cycloaddition of α,β-unsaturated aromatic esters and alkynes constitutes an efficient method for their synthesis. Here, nickel(0) catalysts comprising a chiral bulky C1-symmetric N-heterocyclic carbene ligand were shown to enable an efficient asymmetric synthesis of cyclopentenones from mesityl enoates and internal alkynes under mild conditions. The bulky NHC ligand provided the cyclopentenone products in very high enantioselectivity and led to a regioselective incorporation of unsymmetrically substituted alkynes. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Synthesis of Di- and Trisubstituted Azulenes Using a Danheiser Annulation as the Key Step: An Advanced Organic Laboratory Experiment

    Science.gov (United States)

    Thomas, Rebecca M.; Shea, Kevin M.

    2013-01-01

    This three-week advanced-level organic experiment provides students with an inquiry-based approach focused on learning traditional skills such as primary literature interpretation, reaction design, flash column chromatography, and NMR analysis. Additionally, students address higher-order concepts such as the origin of azulene's blue color,…

  3. Solvent/oxidant-switchable synthesis of multisubstituted quinazolines and benzimidazoles via metal-free selective oxidative annulation of arylamidines.

    Science.gov (United States)

    Lin, Jian-Ping; Zhang, Feng-Hua; Long, Ya-Qiu

    2014-06-06

    A fast and simple divergent synthesis of multisubstituted quinazolines and benzimidazoles was developed from readily available amidines, via iodine(III)-promoted oxidative C(sp(3))-C(sp(2)) and C(sp(2))-N bond formation in nonpolar and polar solvents, respectively. Further selective synthesis of quinazolines in polar solvent was realized by TEMPO-catalyzed sp(3)C-H/sp(2)C-H direct coupling of the amidine with K2S2O8 as the oxidant. No metal, base, or other additives were needed.

  4. Annulated Dialkoxybenzenes as Catholyte Materials for Non-aqueous Redox Flow Batteries: Achieving High Chemical Stability through Bicyclic Substitution

    International Nuclear Information System (INIS)

    Zhang, Jingjing; Yang, Zheng; Shkrob, Ilya A.; Assary, Rajeev S.

    2017-01-01

    1,4-Dimethoxybenzene derivatives are materials of choice for use as catholytes in nonaqueous redox flow batteries, as they exhibit high open-circuit potentials and excellent electrochemical reversibility. However, chemical stability of these materials in their oxidized form needs to be improved. Disubstitution in the arene ring is used to suppress parasitic reactions of their radical cations, but this does not fully prevent ring-addition reactions. By incorporating bicyclic substitutions and ether chains into the dialkoxybenzenes, a novel catholyte molecule, 9,10-bis(2-methoxyethoxy)-1,2,3,4,5,6,7,8-octahydro-1,4:5, 8-dimethanenoanthracene (BODMA), is obtained and exhibits greater solubility and superior chemical stability in the charged state. As a result, a hybrid flow cell containing BODMA is operated for 150 charge–discharge cycles with minimal loss of capacity.

  5. Mechanism and Regioselectivity of Rh(III)-Catalyzed Intermolecular Annulation of Aryl-Substituted Diazenecarboxylates and Alkenes: DFT Insights

    KAUST Repository

    Ajitha, Manjaly John; Huang, Kuo-Wei

    2016-01-01

    is identified as the initial C-H activation, consistent with the previous kinetic studies. Notably, DFT studies offered important insights on the ability of the substrate (diazene carboxylate) to promote the switchable coordination site selectivity during

  6. 20 CFR 416.1835 - Information we need about separation or end of marriage after you become eligible for SSI.

    Science.gov (United States)

    2010-04-01

    ...) Divorce or annulment. If your marriage ends by divorce or annulment, you must show us the decree of divorce or annulment if you can. If you cannot, you must tell us why not and give us whatever evidence you can. (3) Other reason. If your marriage ends for reasons other than death, divorce, or annulment, you...

  7. 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.

  8. A Divergent Mechanistic Course of Pd(0)-Catalyzed Aza-Claisen Rearrangement and Aza-Rautenstrauch-Type Cyclization of N-Allyl-Ynamides

    Science.gov (United States)

    DeKorver, Kyle A.; Hsung, Richard P.; Lohse, Andrew G.; Zhang, Yu

    2010-01-01

    A fascinating mechanistic study of ynamido-palladium-π-allyl complexes is described that features isolation of a unique silyl-ketenimine via aza-Claisen rearrangement, which can be accompanied by an unusual thermal N-to-C 1,3-Ts shift in the formation of tertiary nitriles, and a novel cyclopentenimine formation via a palladium catalyzed aza-Rautenstrauch-type cyclization pathway. PMID:20337418

  9. The First Total Synthesis of Dragmacidin D

    OpenAIRE

    Garg, Neil K.; Sarpong, Richmond; Stoltz, Brian M.

    2002-01-01

    The first total synthesis of the biologically significant bis-indole alkaloid dragmacidin D (5) has been achieved. Thermal and electronic modulation provides the key for a series of palladium-catalyzed Suzuki cross-coupling reactions that furnished the core structure of the complex guanidine- and aminoimidazole-containing dragmacidins. Following this crucial sequence, a succession of meticulously controlled final events was developed leading to the completion of the natural product.

  10. Diversification of indoles via microwave-assisted ligand-free copper-catalyzed N-arylation

    Energy Technology Data Exchange (ETDEWEB)

    Kwon, Jae Kwan; Lee, Jin Hee; Kim, Tae Sung; Yum, Eul Kgun [Dept. of Chemistry, Chu ngnam National University, Daejon (Korea, Republic of); Park, Jee Jung [Western Seoul Center Korea Basic Science Institute, Seoul (Korea, Republic of)

    2016-12-15

    A simple, efficient Cu{sub 2}O catalyst system under microwave irradiation was developed for N-arylation of various indoles without ligands and additives. Diverse N-heteroarylated indoles were prepared by coupling indoles with various heteroaryl halides within 1 h. The selective reactivity of bromoindole with aryl iodide provided N-aryl bromoindoles, which could be useful intermediates for palladium-catalyzed Heck and Suzuki coupling reactions.

  11. Selectivity control in pd-catalyzed c-h functionalization reactions

    OpenAIRE

    Flores Gaspar, Areli

    2013-01-01

    Benzocyclobutenones are an intriguing four-membered ring ketone. In the present thesis, we have developed a new protocol for selectively preparing benzocyclobutenones through intramolecular acylation of aryl bromides via palladium catalyzed C-H bond functionalization reactions based on rac-BINAP ligand. We also found that a subtle modification on the ligand backbone lead to a new catalytic manifold for preparing configurationally-pure styrene derivatives, when using dcpp (bis-dicyclohexylphos...

  12. Synthesis of 2,3-diyne-1,4-naphthoquinone derivatives and evaluation of cytotoxic activity against tumor cell lines

    International Nuclear Information System (INIS)

    Silva, Mauro G.; Camara, Celso A.; Silva, Tania M.S.; Feitosa, Anderson C.S.; Meira, Assuero S.; Pessoa, Claudia

    2013-01-01

    A series of 2,3-diyne-1,4-naphthoquinone derivatives was synthesized from 2,3-dibromo- 1,4-naphthoquinone and various functionalized terminal alkynes using palladium-catalyzed Sonogashira cross-coupling reaction. The diynes were evaluated as potential cytotoxic agents against three tumor cell lines: human ovarian adenocarcinoma (OVCAR-8), human metastatic prostate cancer (PC-3M) and human bronchoalveolar lung carcinoma (NCI-H358M), presenting, in general, satisfactory results for inhibition of cell growth. (author)

  13. Surprisingly Mild Enolate-Counterion-Free Pd(0)-Catalyzed Intramolecular Allylic Alkylations

    DEFF Research Database (Denmark)

    Madec, David; Prestat, Guillaume; Martini, Elisabetta

    2005-01-01

    Palladium-catalyzed intramolecular allylic alkylations of unsaturated EWG-activated amides can take place under phase-transfer conditions or in the presence of a crown ether. These new reaction conditions are milder and higher yielding than those previously reported. A rationalization for such an...... for such an unexpected result is put forth and validated by DFT-B3LYP calculations. The results suggest cyclization via a counterion-free (E)-enolate TS....

  14. Synthesis of 2,3-diyne-1,4-naphthoquinone derivatives and evaluation of cytotoxic activity against tumor cell lines

    Energy Technology Data Exchange (ETDEWEB)

    Silva, Mauro G.; Camara, Celso A.; Silva, Tania M.S., E-mail: ccelso@dcm.ufrpe.br [Universidade Federal Rural de Pernambuco (LSCB/UFRPE), Recife, PE (Brazil). Dept. de Ciencias Moleculares. Lab. de Sintese de Compostos Bioativos; Feitosa, Anderson C.S.; Meira, Assuero S.; Pessoa, Claudia [Universidade Federal do Ceara (LOE/UFC), Fortaleza, CE (Brazil). Dept. de Fisiologia e Farmacologia. Lab. de Oncologia Experimental

    2013-09-15

    A series of 2,3-diyne-1,4-naphthoquinone derivatives was synthesized from 2,3-dibromo- 1,4-naphthoquinone and various functionalized terminal alkynes using palladium-catalyzed Sonogashira cross-coupling reaction. The diynes were evaluated as potential cytotoxic agents against three tumor cell lines: human ovarian adenocarcinoma (OVCAR-8), human metastatic prostate cancer (PC-3M) and human bronchoalveolar lung carcinoma (NCI-H358M), presenting, in general, satisfactory results for inhibition of cell growth. (author)

  15. Synthesis of Secondary Aromatic Amides via Pd-Catalyzed Aminocarbonylation of Aryl Halides Using Carbamoylsilane as an Amide Source.

    Science.gov (United States)

    Tong, Wenting; Cao, Pei; Liu, Yanhong; Chen, Jianxin

    2017-11-03

    Using N-methoxymethyl-N-organylcarbamoyl(trimethyl)silanes as secondary amides source, the direct transformation of aryl halides into the corresponding secondary aromatic amides via palladium-catalyzed aminocarbonylation is described. The reactions tolerated a broad range of functional groups on the aryl ring except big steric hindrance of substituent. The types and the relative position of substituents on the aryl ring impact the coupling efficiency.

  16. Synthesis of novel kavain-like derivatives and evaluation of their cytotoxic activity

    Energy Technology Data Exchange (ETDEWEB)

    Amaral, Patricia de A.; Agustini, Taciane; Eifler-Lima, Vera L. [Universidade Federal do Rio Grande do Sul (UFRGS), Porto Alegre (Brazil). Faculdade de Farmacia. Lab. de Sintese Organica Medicinal; Petrignet, Julien; Cariou, Alexandre; Gree, Rene [Universite de Rennes 1, Rennes (France). Lab. de Chimie Therapeutique; Gouault, Nicolas; Lohezic-Ledevehat, Francoise; David, Michele [CNRS UMR, Universite de Rennes 1, Rennes (France). Lab. de Chimie et Photonique Moleculaires

    2009-07-01

    Palladium-catalyzed cross coupling reactions (Sonogashira-Hagihara, Suzuki-Miyaura, and Heck) coupling and nickel hydride-mediated tandem isomerization aldolisation have been used for the synthesis of three series of {delta}-valerolactones substituted in positions 3, 4, 5 and 6 of the lactone ring. The 26 kavaien-like derivatives were tested against three cell lines and five of them exhibited a weak cytotoxic activity. (author)

  17. One-pot synthesis of 4,8-dibromobenzo[1,2-c;4,5-c']bis[1,2,5]thiadiazole.

    Science.gov (United States)

    Tam, Teck Lip; Li, Hairong; Wei, Fengxia; Tan, Ke Jie; Kloc, Christian; Lam, Yeng Ming; Mhaisalkar, Subodh G; Grimsdale, Andrew C

    2010-08-06

    A one-step synthesis of 4,8-dibromobenzo[1,2-c;4,5-c']bis[1,2,5]thiadiazole with use of 1,2,4,5-tetraaminobenzene tetrahydrobromide and thionyl bromide in good yield is reported. This unit can then be used in the synthesis of low bandgap materials via palladium-catalyzed coupling reactions. The approach offers a quick and easy way to prepare low bandgap materials as compared to the current literature methods.

  18. A broad spectrum catalytic system for removal of toxic organics from water by deep oxidation. Annual progress report, September 15, 1996 - September 14, 1997

    International Nuclear Information System (INIS)

    Sen, A.

    1997-01-01

    'During the first year, the palladium-catalyzed deep oxidation of toxic organics by dioxygen in aqueous solution was examined in some detail. The research performed has established the viability of the catalytic system to effect the deep (and complete) oxidation of a very wide range of organic substrates under mild conditions. One significant observation was that chemical warfare agent models containing phosphorus-carbon and sulfur-carbon bonds could be eliminated by using this procedure.'

  19. Ring-Contraction Strategy for the Practical, Scalable, Catalytic Asymmetric Synthesis of Versatile γ-Quaternary Acylcyclopentenes

    KAUST Repository

    Hong, Allen Y.; Krout, Michael R.; Jensen, Thomas; Bennett, Nathan B.; Harned, Andrew M.; Stoltz, Brian M.

    2011-01-01

    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.

  20. Rh(II-mediated domino [4 + 1]-annulation of α-cyanothioacetamides using diazoesters: A new entry for the synthesis of multisubstituted thiophenes

    Directory of Open Access Journals (Sweden)

    Jury J. Medvedev

    2017-11-01

    Full Text Available A new approach towards the synthesis of multisubstituted thiophenes is elaborated based on Rh(II-catalyzed domino reactions of acyclic diazoesters with α-cyanothioacetamides. It provides a way for the preparation of 5-amino-3-(alkoxycarbonylaminothiophene-2-carboxylates, 2-(5-amino-2-methoxycarbonylthiophene-3-ylaminomalonates and (2-cyano-5-aminothiophene-3-ylcarbamates with the preparative yields of up to 67%. It was also shown that α-cyanothioacetamides easily interact with dirhodium carboxylates to give rather stable 2:1 complexes, resulting in an evident decrease in the efficiency of the catalytic process at moderate temperatures (20–30 °C.

  1. BCl3‐Induced Annulative Oxo‐ and Thioboration for the Formation of C3‐Borylated Benzofurans and Benzothiophenes

    Science.gov (United States)

    Warner, Andrew J.; Churn, Anna; McGough, John S.

    2016-01-01

    Abstract BCl3‐induced borylative cyclization of aryl‐alkynes possessing ortho‐EMe (E=S, O) groups represents a simple, metal‐free method for the formation of C3‐borylated benzothiophenes and benzofurans. The dichloro(heteroaryl)borane primary products can be protected to form synthetically ubiquitous pinacol boronate esters or used in situ in Suzuki–Miyaura cross couplings to generate 2,3‐disubstituted heteroarenes from simple alkyne precursors in one pot. In a number of cases alkyne trans‐haloboration occurs alongside, or instead of, borylative cyclization and the factors controlling the reaction outcome are determined. PMID:27897368

  2. C20H4(C4F8)3: a fluorine-containing annulated corannulene that is a better electron acceptor than C60.

    Science.gov (United States)

    Kuvychko, Igor V; Dubceac, Cristina; Deng, Shihu H M; Wang, Xue-Bin; Granovsky, Alexander A; Popov, Alexey A; Petrukhina, Marina A; Strauss, Steven H; Boltalina, Olga V

    2013-07-15

    At sixes and sevens: The reaction of corannulene with 35 equivalents of 1,4-C4F8I2 is an efficient and a relatively selective process that yields two main products in which six H atoms are substituted with three C4F8 moieties that form six- and seven-membered rings. Low-temperature photoelectron spectroscopy showed the electron affinity of the major isomer (shown) exceeds that of C60 (2.74±0.02 and 2.689±0.008 eV, respectively). Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. N-Annulated perylene-substituted and fused porphyrin dimers with intense near-infrared one-photon and two-photon absorption

    KAUST Repository

    Luo, Jie; Lee, Sangsu; Son, Minjung; Zheng, Bin; Huang, Kuo-Wei; Qi, Qingbiao; Zeng, Wangdong; Li, Gongqiang; Kim, Dongho; Wu, Jishan

    2015-01-01

    . These new chromophores also exhibited good nonlinear optical susceptibility with large two-photon absorption cross-sections in the NIR region due to extended π-conjugation. Time-dependent density functional theory calculations have been performed to aid our

  4. One-pot synthesis of spiropyrroloquinoline-isoindolinone and their aza-analogs via the Ugi-4CR/metal-free intramolecular bis-annulation process.

    Science.gov (United States)

    Ghandi, Mehdi; Zarezadeh, Nahid; Abbasi, Alireza

    2015-08-14

    This presentation discloses a one-pot synthesis of a series of spiropyrroloquinoline isoindolinone and spiropyrroloquinoline aza-isoindolinone scaffolds. The reaction proceeds by the combination of a Ugi four-component reaction (4CR) and two intramolecular cyclizations under metal-free conditions. The proof of the structures relies on analytical investigation and X-ray crystallography.

  5. One-pot synthesis of multisubstituted 2-aminoquinolines from annulation of 1-aryl tetrazoles with internal alkynes via double C-H activation and denitrogenation.

    Science.gov (United States)

    Zhang, Lei; Zheng, Liyao; Guo, Biao; Hua, Ruimao

    2014-12-05

    An efficient, one-pot synthesis of multisubstituted 2-aminoquinolines from 1-aryl tetrazoles and internal alkynes has been developed. The reaction involves cyclization of 1-aryl tetrazoles with internal alkynes via rhodium(III)-catalyzed double C-H activation and copper(II)-mediated denitrogenation.

  6. Eosin Y photoredox catalyzed net redox neutral reaction for regiospecific annulation to 3-sulfonylindoles via anion oxidation of sodium sulfinate salts.

    Science.gov (United States)

    Rohokale, Rajendra S; Tambe, Shrikant D; Kshirsagar, Umesh A

    2018-01-24

    An eosin Y photoredox catalyzed net redox neutral process for 3-sulfonylindoles via the anionic oxidation of sodium sulfinate salts and its radical cascade cyclization with 2-alkynyl-azidoarenes was developed with visible light as a mediator. The reaction offers metal and oxidant/reductant free, visible light mediated vicinal sulfonamination of alkynes to 2-aryl/alkyl-3-sulfonylindoles and proceeds via the generation of a sulfur-centered radical through direct oxidation of the sulfinate anion by an excited photocatalyst with a reductive quenching cycle. The mild conditions, use of an organic dye as photo-catalyst, bench stability and easily accessible starting materials make the present approach green and attractive.

  7. Identification, characterization, and in vitro culture of highly divergent arenaviruses from boa constrictors and annulated tree boas: candidate etiological agents for snake inclusion body disease.

    Science.gov (United States)

    Stenglein, Mark D; Sanders, Chris; Kistler, Amy L; Ruby, J Graham; Franco, Jessica Y; Reavill, Drury R; Dunker, Freeland; Derisi, Joseph L

    2012-01-01

    Inclusion body disease (IBD) is an infectious fatal disease of snakes typified by behavioral abnormalities, wasting, and secondary infections. At a histopathological level, the disease is identified by the presence of large eosinophilic cytoplasmic inclusions in multiple tissues. To date, no virus or other pathogen has been definitively characterized or associated with the disease. Using a metagenomic approach to search for candidate etiologic agents in snakes with confirmed IBD, we identified and de novo assembled the complete genomic sequences of two viruses related to arenaviruses, and a third arenavirus-like sequence was discovered by screening an additional set of samples. A continuous boa constrictor cell line was established and used to propagate and isolate one of the viruses in culture. Viral nucleoprotein was localized and concentrated within large cytoplasmic inclusions in infected cells in culture and tissues from diseased snakes. In total, viral RNA was detected in 6/8 confirmed IBD cases and 0/18 controls. These viruses have a typical arenavirus genome organization but are highly divergent, belonging to a lineage separate from that of the Old and New World arenaviruses. Furthermore, these viruses encode envelope glycoproteins that are more similar to those of filoviruses than to those of other arenaviruses. These findings implicate these viruses as candidate etiologic agents of IBD. The presence of arenaviruses outside mammals reveals that these viruses infect an unexpectedly broad range of species and represent a new reservoir of potential human pathogens. Inclusion body disease (IBD) is a common infectious disease of captive snakes. IBD is fatal and can cause the loss of entire animal collections. The cause of the disease has remained elusive, and no treatment exists. In addition to being important to pet owners, veterinarians, breeders, zoological parks, and aquariums, the study of animal disease is significant since animals are the source of virtually every emerging infectious human disease. We searched for candidate causative agents in snakes diagnosed with IBD and found a group of novel viruses distantly related mainly to arenaviruses but also to filoviruses, both of which can cause fatal hemorrhagic fevers when transmitted from animals to humans. In addition to providing evidence that strongly suggests that these viruses cause snake IBD, this discovery reveals a new and unanticipated domain of virus biology and evolution.

  8. Dual overcharge protection and solid electrolyte interphase-improving action in Li-ion cells containing a bis -annulated dialkoxyarene electrolyte additive

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Jingjing; Shkrob, Ilya A.; Assary, Rajeev S.; Zhang, Shuo; Hu, Bin; Liao, Chen; Zhang, Zhengcheng; Zhang, Lu

    2018-02-01

    We demonstrate that 9,10-Bis(2-methoxyethoxy)-1,2,3,4,5,6,7,8-octahydro-1,4:5,8-dimethanoanthracene redox shuttle molecule survives over 120 cycles with 100% overcharge ratio at C/5 rate in litium-ion batteries. Equally remarkably, in the presence of this electrolyte additive, the cell impedance becomes significantly lower compared to the control cells without this additive during the formation, normal cycling, and even under overcharge conditions.

  9. CuI/Pd0 cooperative dual catalysis: tunable stereoselective construction of tetra-substituted alkenes.

    Science.gov (United States)

    Vercruysse, Sébastien; Cornelissen, Loïc; Nahra, Fady; Collard, Laurent; Riant, Olivier

    2014-02-10

    This paper describes a tunable and stereoselective dual catalytic system that uses copper and palladium reagents. This cooperative silylcupration and palladium-catalyzed allylation readily affords trisubstituted alkenylsilanes. Fine-tuning the reaction conditions allows selective access to one stereoisomer over the other. This new methodology tolerates different substituents on both coupling partners with high levels of stereoselectivity. The one-pot reaction involving a Cu(I)/Pd(0) cooperative dual catalyst directly addresses the need to develop more time-efficient and less-wasteful synthetic pathways. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Removal of amino groups from anilines through diazonium salt-based reactions.

    Science.gov (United States)

    He, Linman; Qiu, Guanyinsheng; Gao, Yueqiu; Wu, Jie

    2014-09-28

    This minireview describes the applications of in situ generated diazonium salts from anilines in organic synthesis. In situ generation of diazonium salts from anilines represents an efficient and practical pathway, leading to a series of useful structures. In these transformations, the amino group of aniline formally acts as a leaving group. Two distinctive kinds of mechanisms, including transition metal (especially palladium)-catalyzed oxidative addition-reductive elimination and a radical process, are involved in the removal of amino groups from anilines, and both catalytic processes are described in this minireview.

  11. α-Oxo-Ketenimines from Isocyanides and α-Haloketones: Synthesis and Divergent Reactivity.

    Science.gov (United States)

    Mamboury, Mathias; Wang, Qian; Zhu, Jieping

    2017-09-18

    The palladium-catalyzed reaction of α-haloketones with isocyanides afforded α-oxo-ketenimines through β-hydride elimination of the β-oxo-imidoyl palladium intermediates. Reaction of these relatively stable α-oxo-ketenimines with nucleophiles such as hydrazines, hydrazoic acid, amines, and Grignard reagent afforded pyrazoles, tetrazole, β-keto amidines, and enaminone, respectively, with high chemoselectivity. Whereas amines attack exclusively on the ketenimine functions, the formal [3+2] cycloaddition between N-monosubstituted hydrazines and α-oxo-ketenimines was initiated by nucleophilic addition to the carbonyl group. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Excess Sodium Tetraphenylborate and Intermediates Decomposition Studies

    Energy Technology Data Exchange (ETDEWEB)

    Barnes, M.J.

    1998-12-07

    The stability of excess amounts of sodium tetraphenylborate (NaTPB) in the In-Tank Precipitation (ITP) facility depends on a number of variables. Concentration of palladium, initial benzene, and sodium ion as well as temperature provide the best opportunities for controlling the decomposition rate. This study examined the influence of these four variable on the reactivity of palladium-catalyzed sodium tetraphenylborate decomposition. Also, single effects tests investigated the reactivity of simulants with continuous stirring and nitrogen ventilation, with very high benzene concentrations, under washed sodium concentrations, with very high palladium concentrations, and with minimal quantities of excess NaTPB.

  13. Domino approach to 2-aroyltrimethoxyindoles as novel heterocyclic combretastatin A4 analogues.

    Science.gov (United States)

    Arthuis, Martin; Pontikis, Renée; Chabot, Guy G; Quentin, Lionel; Scherman, Daniel; Florent, Jean-Claude

    2011-01-01

    Two series of 2-aroyltrimethoxyindoles were designed to investigate the effects of the replacement of the trimethoxyphenyl ring of phenstatin with a trimethoxyindole moiety. These compounds were efficiently prepared through a domino palladium-catalyzed sequence from 2-gem-dibromovinylanilines substituted by three methoxy groups and arylboronic acids under carbon monoxide atmosphere. These novel heterocyclic combretastatin A4 analogues were evaluated for their cell growth inhibitory properties and their ability to inhibit the tubulin polymerization. Copyright © 2010 Elsevier Masson SAS. All rights reserved.

  14. Highly twisted 1,2:8,9-dibenzozethrenes: Synthesis, ground state, and physical properties

    KAUST Repository

    Sun, Zhe; Zheng, Bin; Hu, Pan; Huang, Kuo-Wei; Wu, Jishan

    2014-01-01

    Two soluble and stable 1,2:8,9-dibenzozethrene derivatives (3a,b) are synthesized through a palladium-catalyzed cyclodimerization reaction. X-ray crystallographic analysis shows that these molecules are highly twisted owing to congestion at the cove region. Broken-symmetry DFT calculations predict that they have a singlet biradical ground state with a smaller biradical character and a large singlet-triplet energy gap; these predictions are supported by NMR and electronic absorption measurements. They have small energy gaps and exhibit farred/near-infrared absorption/emission and amphoteric redox behaviors.

  15. Modeling of hydrogen/deuterium dynamics and heat generation on palladium nanoparticles for hydrogen storage and solid-state nuclear fusion

    Directory of Open Access Journals (Sweden)

    Katsuaki Tanabe

    2016-01-01

    Full Text Available We modeled the dynamics of hydrogen and deuterium adsorbed on palladium nanoparticles including the heat generation induced by the chemical adsorption and desorption, as well as palladium-catalyzed reactions. Our calculations based on the proposed model reproduce the experimental time-evolution of pressure and temperature with a single set of fitting parameters for hydrogen and deuterium injection. The model we generated with a highly generalized set of formulations can be applied for any combination of a gas species and a catalytic adsorbent/absorbent. Our model can be used as a basis for future research into hydrogen storage and solid-state nuclear fusion technologies.

  16. Tandem catalytic allylic amination and [2,3]-Stevens rearrangement of tertiary amines.

    Science.gov (United States)

    Soheili, Arash; Tambar, Uttam K

    2011-08-24

    We have developed a catalytic allylic amination involving tertiary aminoesters and allylcarbonates, which is the first example of the use of tertiary amines as intermolecular nucleophiles in metal-catalyzed allylic substitution chemistry. This process is employed in a tandem ammonium ylide generation/[2,3]-rearrangement reaction, which formally represents a palladium-catalyzed Stevens rearrangement. Low catalyst loadings and mild reaction conditions are compatible with an unprecedented substrate scope for the ammonium ylide functionality, and products are generated in high yields and diastereoselectivities. Mechanistic studies suggested the reversible formation of an ammonium intermediate.

  17. Stereoselective synthesis of functionalized cyclic amino acid derivatives via a [2,3]-Stevens rearrangement and ring-closing metathesis.

    Science.gov (United States)

    Nash, Aaron; Soheili, Arash; Tambar, Uttam K

    2013-09-20

    Unnatural cyclic amino acids are valuable tools in biomedical research and drug discovery. A two-step stereoselective strategy for converting simple glycine-derived aminoesters into unnatural cyclic amino acid derivatives has been developed. The process includes a palladium-catalyzed tandem allylic amination/[2,3]-Stevens rearrangement followed by a ruthenium-catalyzed ring-closing metathesis. The [2,3]-rearrangement proceeds with high diastereoselectivity through an exo transition state. Oppolzer's chiral auxiliary was utilized to access an enantiopure cyclic amino acid by this approach, which will enable future biological applications.

  18. Pd(OAc)2/Ph3P-catalyzed dimerization of isoprene and synthesis of monoterpenic heterocycles.

    Science.gov (United States)

    Kellner, Dominik; Weger, Maximilian; Gini, Andrea; Mancheño, Olga García

    2017-01-01

    The palladium-catalyzed dimerization of isoprene is a practical approach of synthesizing monoterpenes. Though several highly selective methods have been reported, most of them still required pressure or costly ligands for attaining the active system and desired selectivity. Herein, we present a simple and economical procedure towards the tail-to-tail dimer using readily available Pd(OAc) 2 and inexpensive triphenylphosphine as ligand. Furthermore, simple screw cap vials are employed, allowing carrying out the reaction at low pressure. In addition, the potential of the dimer as a chemical platform for the preparation of heterocyclic terpenes by subsequent (hetero)-Diels-Alder or [4 + 1]-cycloadditions with nitrenes is also depicted.

  19. Heteroaryl ethers by oxidative palladium catalysis of pyridotriazol-1-yloxy pyrimidines with arylboronic acids.

    Science.gov (United States)

    Bardhan, Sujata; Wacharasindhu, Sumrit; Wan, Zhao-Kui; Mansour, Tarek S

    2009-06-18

    The oxidative palladium-catalyzed cross-coupling of pyrimidines containing pyridotriazol-1-yloxy (OPt) as either a urea or an amide functional group with arylboronic acids in the presence of Cs(2)CO(3) in DME containing 0.6-1.0% H(2)O is described for the preparation of heteroaryl ethers. The bromo substitution in the case of 3-(5-bromo-pyrimidin-2-yloxy)-3H-[1,2,3]triazolo[4,5-b]pyridine 1 could serve as a handle for further elaborations such as Suzuki coupling for attaching varied aryl groups.

  20. Regiospecific decarboxylative allylation of nitriles

    Science.gov (United States)

    Recio, Antonio; Tunge, Jon A.

    2009-01-01

    Palladium-catalyzed decarboxylative α-allylation of nitriles readily occurs using Pd2(dba)3 and rac-BINAP. This catalyst mixture also allows the highly regiospecific α-allylation of nitriles in the presence of much more acidic α-protons. Thus, the reported method provides access to compounds that are not readily available via base-mediated allylation chemistries. Lastly, mechanistic investigations indicate that there is a competition between C- and N-allylation of an intermediate nitrile-stabilized anion and that N-allylation is followed by a rapid [3,3]-sigmatropic rearrangement. PMID:19921827

  1. Palladium(II)-catalyzed ortho-C-H arylation/alkylation of N-benzoyl α-amino ester derivatives.

    Science.gov (United States)

    Misal Castro, Luis C; Chatani, Naoto

    2014-04-14

    The palladium-catalyzed arylation/alkylation of ortho-C-H bonds in N-benzoyl α-amino ester derivatives is described. In such a system both the NH-amido and the CO2R groups in the α-amino ester moieties play a role in successful C-H activation/C-C bond formation using iodoaryl coupling partners. A wide variety of functional groups and electron-rich/deficient iodoarenes are tolerated. The yields obtained range from 20 to 95%. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Aerobic Transition-Metal-Free Synthesis of 2,3-Diarylindoles and 5-Aryluracils via Oxidative Nucleophilic Substitution of Hydrogen Pathway

    Energy Technology Data Exchange (ETDEWEB)

    Yu, Jin; Moon, Hye Ran; Kim, Su Yeon; Kim, Jae Nyoung [Chonnam National Un iversity, Gwangju (Korea, Republic of)

    2016-01-15

    2,3-diarylindoles and 5-aryluracils were synthesized by ONSH pathway under transition-metal-free conditions in good to moderate yields using molecular oxygen as an oxidant. As 2,3-diarylindoles have been found in many biologically important compounds, the synthesis of this scaffold has received much attention. Most frequently, 2,3-diarylindoles have been prepared via palladium-catalyzed arylations of 2-arylindole with bromoarenes. During our recent transition metal-catalyzed arylations of indoles and uracils, we were interested in the arylation in the absence of an expensive transition metal catalyst.

  3. Efficient total synthesis of (S)-14-azacamptothecin.

    Science.gov (United States)

    Liu, Guan-Sai; Yao, Yuan-Shan; Xu, Peng; Wang, Shaozhong; Yao, Zhu-Jun

    2010-06-01

    An efficient total synthesis of (S)-14-azacamptothecin has been accomplished in 10 steps and 56% overall yield from 5H-pyrano[4,3-d]pyrimidine 8. A mild Hendrickson reagent-triggered intramolecular cascade cyclization, a highly enantioselective dihydroxylation, and an efficient palladium-catalyzed transformation of an O-allyl into N-allyl group are the key steps in the synthesis. This work provides a much higher overall yield than the previous achievement and shows sound flexibility for the further applications that will lead to new bioactive analogues.

  4. Synthesis of new enantiopure poly(hydroxyaminooxepanes as building blocks for multivalent carbohydrate mimetics

    Directory of Open Access Journals (Sweden)

    Léa Bouché

    2014-01-01

    Full Text Available New compounds with carbohydrate-similar structure (carbohydrate mimetics are presented in this article. Starting from enantiopure nitrones and lithiated TMSE-allene we prepared three 1,2-oxazine derivatives which underwent a highly stereoselective Lewis acid-induced rearrangement to give bicyclic products in good yield. Subsequent reductive transformations delivered a library of new poly(hydroxyaminooxepane derivatives. The crucial final palladium-catalyzed hydrogenolysis of the 1,2-oxazine moiety was optimized resulting in a reasonably efficient approach to a series of new seven-membered carbohydrate mimetics.

  5. Combining cycloisomerization with trienamine catalysis: a regiochemically flexible enantio- and diastereoselective synthesis of hexahydroindoles.

    Science.gov (United States)

    Chintalapudi, V; Galvin, E A; Greenaway, R L; Anderson, E A

    2016-01-14

    The synthesis of polysubstituted hexahydroindoles through trienamine-organocatalyzed cycloadditions of pyrrolidinyl dienals, prepared by palladium-catalyzed cycloisomerization, is reported. The cycloadditions of this novel class of dienals proceed with excellent levels of enantio- and diastereoselectivity, with the regioselectivity of cycloaddition with respect to the tethering ring readily tuned through design of the cycloisomerization substrate. This work culminates in the first examples of double-stereodifferentiating trienamine catalysis, where catalyst stereocontrol dominates facial selectivity in the cycloaddition, affording azacyclic products that are specifically functionalized at every position.

  6. NMR as a tool for kinetic studies: application to the assessment of organo tin reactivity

    Energy Technology Data Exchange (ETDEWEB)

    Fouquet, E.; Roulet, T. [Bordeaux-1 Univ., 33 - Talence (France); Pianet, I. [Bordeaux-1 Univ., 33 -Talence (France) CNRS, Centre d`Etudes Structurales et d`Analyse des Molecules Organiques; Willem, R. [Brussels University (VUB), Brussels (Belgium)

    1998-02-01

    There is a growing interest for the research of an answer to the environmental problems related to the industrial use of tetra organo tins. An interesting alternative would be to develop the chemistry of mono organo tins because of their lower toxicity and of the easy removal of ``inorganic`` tin side products. In this work, halogen exchange rates are measured for various mono organo tins with NMR techniques (EXSY spectra and 1 D {sup 119} Sn NMR), and an exchange mechanism is proposed. A correlation between kinetic data and the reactivity of the mono organo tins is then exemplified with radical allylic transfer and palladium catalyzed coupling reactions. (authors) 14 refs.

  7. 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.

  8. Donor-Acceptor Chromophores based on Acetylenic Scaffolds and Indenofluorenes

    DEFF Research Database (Denmark)

    Christensen, Mikkel Andreas

    -valence salt). [BILLEDE UDELADT] In the third chapter the reactivity of chloroalkynes is explored. A number of chloroalkynes is prepared and subjected to palladium-catalyzed cross coupling with a terminal alkyne. The chloroalkynes turned out to couple very well using the same conditions as for the Sonogashira...... cross-coupling. The reactivity of chloroalkynes was compared to that of Sonogashira substrates and the chloroalkynes turned out to react as fast as an aryl iodide. Some of the couplings gave reductive homo-coupling of the chloroalkyne as a byproducts. This was avoided by using a large copper...

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

    KAUST Repository

    Stoltz, Brian; McDougal, Nolan; Virgil, Scott

    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.

  10. A chemical probe for the estrogen receptor: synthesis of the 3H-isotopomer of raloxifene

    International Nuclear Information System (INIS)

    Dodge, J.A.; Stocksdale, M.G.; Jones, C.D.

    1995-01-01

    Radiolabelled raloxifene (LY 156758) has been prepared by tritium gas hydrogenolysis of a 3-aroyl-bis-brominated precursor. The requisite halogenated intermediate was accessed by regioselective aroylation of benzothiophene with the acid chloride of 3,5-dibromo-4-[2-(1-piperdinyl)ethoxy]benzoic acid. Selective deprotection of the aryl methyl ethers in the presence of the ethoxy side-chain followed by palladium catalyzed halogen-tritium exchange provided the target compound with a specific activity of 30.1 Ci/mmol. (author)

  11. Highly twisted 1,2:8,9-dibenzozethrenes: Synthesis, ground state, and physical properties

    KAUST Repository

    Sun, Zhe

    2014-08-08

    Two soluble and stable 1,2:8,9-dibenzozethrene derivatives (3a,b) are synthesized through a palladium-catalyzed cyclodimerization reaction. X-ray crystallographic analysis shows that these molecules are highly twisted owing to congestion at the cove region. Broken-symmetry DFT calculations predict that they have a singlet biradical ground state with a smaller biradical character and a large singlet-triplet energy gap; these predictions are supported by NMR and electronic absorption measurements. They have small energy gaps and exhibit farred/near-infrared absorption/emission and amphoteric redox behaviors.

  12. Oligo(naphthylene–ethynylene) Molecular Rods

    DEFF Research Database (Denmark)

    Cramer, Jacob Roland; Ning, Yanxiao; Shen, Cai

    2013-01-01

    of palladium-catalyzed Sonogashira reactions between naphthyl halides and acetylenes. The triazene functionality was used as a protected iodine precursor to allow linear extension of the molecular rods during the synthe-ses. The carboxylic acid groups in the target molecules were protected as esters during......Molecular rods designed for surface chirality studies have been synthesized in high yields. The molecules are composed of oligo(naphthylene–ethynylene) skeletons and functionalized at their two termini with carboxylic acids and hydrophobic groups. The molecular skeletons were constructed by means...

  13. Thiocarbamate-Directed Tandem Olefination-Intramolecular Sulfuration of Two Ortho C-H Bonds: Application to Synthesis of a COX-2 Inhibitor.

    Science.gov (United States)

    Li, Wendong; Zhao, Yingwei; Mai, Shaoyu; Song, Qiuling

    2018-02-16

    A palladium-catalyzed dual ortho C-H bond activation of aryl thiocarbamates is developed. This tandem reaction initiates by thiocarbamate-directed ortho C-H palladation, which leads to favorable olefin insertion rather than reductive elimination. The oxidative Heck reaction followed by another C-H activation and sulfuration affords the dual-functionalized products. This reaction provides a concise route to the S,O,C multisubstituted benzene skeleton which could be successfully applied for the synthesis of a COX-2 inhibitor.

  14. P(O)R2-Directed Enantioselective C-H Olefination toward Chiral Atropoisomeric Phosphine-Olefin Compounds.

    Science.gov (United States)

    Li, Shi-Xia; Ma, Yan-Na; Yang, Shang-Dong

    2017-04-07

    An effective synthesis of chiral atropoisomeric biaryl phosphine-olefin compounds via palladium-catalyzed enantioselective C-H olefination has been developed for the first time. The reactions are operationally simple, tolerate wide functional groups, and have a good ee value. Notably, P(O)R 2 not only acts as the directing group to direct C-H activation in order to make a useful ligand but also serves to facilitate composition of the product in a useful manner in this transformation.

  15. Transmissive Olefination Route to Putative “Morinol I” Lignans

    Science.gov (United States)

    Yao, Lihua; Pitta, Bhaskar; Ravikumar, P. C.; Purzycki, Matthew; Fleming, Fraser F.

    2012-01-01

    A series of morinol-type lignans were rapidly assembled using a Grignard-based transmissive olefination. In combination with palladium-catalyzed arylations, the strategy provides stereoselective access to (7Z, 7′E), (7E, 7′E), (7E, 7′Z) morinol diastereomers and the (7Z, 8′E) and (7E, 8′E) conjugated analogs. Critical for the E/Z-stereoselectivity is a new, general method for converting alkenenitriles to alkenemethanols that circumvents the enal E/Z isomerization commonly encountered during conventional i-Bu2AlH reduction. PMID:22432777

  16. Palladium(II)-Catalyzed meta-C-H Olefination: Constructing Multisubstituted Arenes through Homo-Diolefination and Sequential Hetero-Diolefination.

    Science.gov (United States)

    Bera, Milan; Maji, Arun; Sahoo, Santosh K; Maiti, Debabrata

    2015-07-13

    Divinylbenzene derivatives represent an important class of molecular building blocks in organic chemistry and materials science. Reported herein is the palladium-catalyzed synthesis of divinylbenzenes by meta-C-H olefination of sulfone-based arenes. Successful sequential olefinations in a position-selective manner provided a novel route for the synthesis of hetero-dialkenylated products, which are difficult to access using conventional methods. Additionally, 1,3,5-trialkenylated compounds can be generated upon successful removal of the directing group. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. m-[125I]iodoaniline: a useful reagent for radiolabeling biotin

    International Nuclear Information System (INIS)

    Khawli, L.A.; Kassis, A.I.

    1992-01-01

    Biotinyl-m-[ 125 I]iodoanilide (BIA) was synthesized by coupling biotin to m-[ 125 I]iodoaniline via a mixed anhydride reaction. m-[ 125 I]Iodoaniline was produced from the tin precursor, which was prepared using a palladium catalyzed reaction of hexabutylditin with m-bromoaniline. The radioiodinated BIA derivative is characterized by a stable amide and/or intact ureido group on the biotin molecule, it may thus be a useful carrier for targeting radionuclides to avidin-conjugated antibodies previously localized on tumors. (author)

  18. A concise, efficient synthesis of sugar-based benzothiazoles through chemoselective intramolecular C-S coupling

    KAUST Repository

    Shen, Chao

    2012-01-01

    Sugar-based benzothiazoles are a new class of molecules promising for many biological applications. Here, we have synthesized a wide range of sugar-based benzothiazoles from readily accessible glycosyl thioureas by chemoselective, palladium-catalyzed C-S coupling reactions. Corroborated by theoretical calculations, a mechanistic investigation indicates that the coordination to the palladium by a pivaloyl carbonyl group and the presence of intramolecular hydrogen bonding play important roles in the efficiency and chemoselectivity of reaction. These fluorescent glycoconjugates can be observed to readily enter mammalian tumor cells and exhibit potential in vitro antitumor activity. This journal is © The Royal Society of Chemistry 2012.

  19. Primary Alcohols from Terminal Olefins: Formal Anti-Markovnikov Hydration via Triple Relay Catalysis

    KAUST Repository

    Dong, G.

    2011-09-15

    Alcohol synthesis is critical to the chemical and pharmaceutical industries. The addition of water across olefins to form primary alcohols (anti-Markovnikov olefin hydration) would be a broadly useful reaction but has largely proven elusive; an indirect hydroboration/oxidation sequence requiring stoichiometric borane and oxidant is currently the most practical methodology. Here, we report a more direct approach with the use of a triple relay catalysis system that couples palladium-catalyzed oxidation, acid-catalyzed hydrolysis, and ruthenium-catalyzed reduction cycles. Aryl-substituted terminal olefins are converted to primary alcohols by net reaction with water in good yield and excellent regioselectivity.

  20. Modeling of hydrogen/deuterium dynamics and heat generation on palladium nanoparticles for hydrogen storage and solid-state nuclear fusion.

    Science.gov (United States)

    Tanabe, Katsuaki

    2016-01-01

    We modeled the dynamics of hydrogen and deuterium adsorbed on palladium nanoparticles including the heat generation induced by the chemical adsorption and desorption, as well as palladium-catalyzed reactions. Our calculations based on the proposed model reproduce the experimental time-evolution of pressure and temperature with a single set of fitting parameters for hydrogen and deuterium injection. The model we generated with a highly generalized set of formulations can be applied for any combination of a gas species and a catalytic adsorbent/absorbent. Our model can be used as a basis for future research into hydrogen storage and solid-state nuclear fusion technologies.

  1. Technical specifications (replaces note T.62). Irradiation of graphite at ambient temperature, Note T. 76; Specification technique, (Annule et remplace la note T. 62), Irradiation de graphite a temperature ambiante, Note T. 76

    Energy Technology Data Exchange (ETDEWEB)

    Reseau, R A [Services des grandes piles experimentales, Section ' Physique et Experimentation, Saclay (France)

    1962-12-15

    The objective is to study the effects of fast neutron irradiation of different graphite samples. The irradiation conditions should be as follows: integral fast neutron flux should be higher than 10{sup 20} neutrons/cm{sup 2}, the reactor should operate at steady state for 15 days, the temperature od samples should not be higher than 100 deg C, preferably 80 deg C. Note T. 62 which is replaced by this Note is attached.

  2. Impact of the Valence Charge of Transition Metals on the Cobalt- and Rhodium-Catalyzed Synthesis of Indenamines, Indenols, and Isoquinolinium Salts: A Catalytic Cycle Involving MIII/MV [M = Co, Rh] for [4+2] Annulation.

    Science.gov (United States)

    Chiou, Mong-Feng; Jayakumar, Jayachandran; Cheng, Chien-Hong; Chuang, Shih-Ching

    2018-06-13

    Reaction mechanisms for the synthesis of indenamines, indenols, and isoquinolinium salts through cobalt- and rhodium-catalysis were investigated using density functional theory calculations. We found that the valence charge of transition metals dramatically influences the reaction pathways. Catalytic reactions involving lower-oxidation-state transition metals (M I /M III , M = Co and Rh) generally favor a [3+2] cyclization pathway, whereas those involving higher oxidation states (M III /M V ) proceed through a [4+2] cyclization pathway. A catalytic cycle with novel M III /M V as a crucial species was successfully revealed for isoquinolinium salts synthesis, which highly valent M V was not only encountered in the [RhCp*]-catalysis but also in the [CoCp*]-catalysis.

  3. Hybrid macrocycle formation and spiro annulation on cis-syn-cis-tricyclo[6.3.0.02,6]undeca-3,11-dione and its congeners via ring-closing metathesis

    Directory of Open Access Journals (Sweden)

    Sambasivarao Kotha

    2015-07-01

    Full Text Available We have developed a simple methodology to transform cis-syn-cis-triquinane derivative 2 into the diindole based macrocycle 6 involving Fischer indolization and ring-closing metathesis (RCM. Various spiro-polyquinane derivatives have been assembled via RCM as a key step.

  4. Total Synthesis of ent-Pregnanolone Sulfate and Its Biological Investigation at the NMDA Receptor

    Czech Academy of Sciences Publication Activity Database

    Kapras, Vojtěch; Vyklický, Vojtěch; Buděšínský, Miloš; Císařová, I.; Vyklický ml., Ladislav; Chodounská, Hana; Jahn, Ullrich

    2018-01-01

    Roč. 20, č. 4 (2018), s. 946-949 ISSN 1523-7060 R&D Projects: GA ČR(CZ) GBP304/12/G069; GA TA ČR(CZ) TE01020028; GA MZd(CZ) NV15-29370A Grant - others:AV ČR(CZ) MSM200111601 Program:Program na podporu mezinárodní spolupráce začínajících výzkumných pracovníků Institutional support: RVO:61388963 ; RVO:67985823 Keywords : Wieland-Miescher ketone * palladium-catalyzed reduction * neuroactive steroids Subject RIV: CC - Organic Chemistry OBOR OECD: Organic chemistry Impact factor: 6.579, year: 2016

  5. Evolution of a strategy for preparing bioactive small molecules by sequential multicomponent assembly processes, cyclizations, and diversification.

    Science.gov (United States)

    Sahn, James J; Granger, Brett A; Martin, Stephen F

    2014-10-21

    A strategy for generating diverse collections of small molecules has been developed that features a multicomponent assembly process (MCAP) to efficiently construct a variety of intermediates possessing an aryl aminomethyl subunit. These key compounds are then transformed via selective ring-forming reactions into heterocyclic scaffolds, each of which possesses suitable functional handles for further derivatizations and palladium-catalyzed cross coupling reactions. The modular nature of this approach enables the facile construction of libraries of polycyclic compounds bearing a broad range of substituents and substitution patterns for biological evaluation. Screening of several compound libraries thus produced has revealed a large subset of compounds that exhibit a broad spectrum of medicinally-relevant activities.

  6. Synthesis of a series of soluble main-chain chiral nonracemic poly(alkyl-aryl ketone

    Directory of Open Access Journals (Sweden)

    2008-06-01

    Full Text Available A series of main-chain chiral polyketones have been synthesized through condensation polymerization of a dihalide and a diketone with optically pure binaphthyl moiety as linkage in the polymer backbone. The solubility of the polymers can be easily enhanced by substituents at the alpha position next to the carbonyl groups. Reducing the steric hindrance of the substituents in the monomers increases the reactivity of the polymerization. The chiral polymers exhibit large optical rotations. Circular Dichroism (CD spectra of the polymers are similar to those of the corresponding monomers. The novel synthetic strategy may have great impact on future development of palladium catalyzed condensation polymerizations. The highly soluble chiral polymers synthesized allow for preparation of materials in the form of thin films and have potentials applications in various areas such as chiral separation and recognition.

  7. Bedford-type palladacycle catalyzed Miyaura-borylation of aryl halides with tetrahydroxydiboron in water

    KAUST Repository

    Zernickel, Anna; Du, Weiyuan; Ghorpade, Seema; Sawant, Dinesh Nanaji; Makki, Arwa; Sekar, Nagaiyan; Eppinger, Jö rg

    2018-01-01

    A mild aqueous protocol for palladium catalyzed Miyaura borylation of aryl iodides, aryl bromides and aryl chlorides with tetrahydroxydiboron (BBA) as a borylating agent is developed. The developed methodology requires low catalyst loading of Bedford-type palladacycle catalyst (0.05 mol %) and works best under mild reaction conditions at 40 °C in short time of 6 hours in water. In addition, our studies show that for Miyaura borylation using BBA in aqueous condition, maintaining a neutral reaction pH is very important for reproducibility and higher yields of corresponding borylated products. Moreover, our protocol is applicable for a broad range of aryl halides, corresponding borylated products are obtained in excellent yields up to 93% with 29 examples demonstrating its broad utility and functional group tolerance.

  8. Pd(OAc2/Ph3P-catalyzed dimerization of isoprene and synthesis of monoterpenic heterocycles

    Directory of Open Access Journals (Sweden)

    Dominik Kellner

    2017-08-01

    Full Text Available The palladium-catalyzed dimerization of isoprene is a practical approach of synthesizing monoterpenes. Though several highly selective methods have been reported, most of them still required pressure or costly ligands for attaining the active system and desired selectivity. Herein, we present a simple and economical procedure towards the tail-to-tail dimer using readily available Pd(OAc2 and inexpensive triphenylphosphine as ligand. Furthermore, simple screw cap vials are employed, allowing carrying out the reaction at low pressure. In addition, the potential of the dimer as a chemical platform for the preparation of heterocyclic terpenes by subsequent (hetero-Diels–Alder or [4 + 1]-cycloadditions with nitrenes is also depicted.

  9. Push-pull quinoidal porphyrins.

    Science.gov (United States)

    Smith, Martin J; Blake, Iain M; Clegg, William; Anderson, Harry L

    2018-05-01

    A family of push-pull quinoidal porphyrin monomers has been prepared from a meso-formyl porphyrin by bromination, thioacetal formation, palladium-catalyzed coupling with malononitrile and oxidation with DDQ. Attempts at extending this synthesis to a push-pull quinoidal/cumulenic porphyrin dimer were not successful. The crystal structures of the quinoidal porphyrins indicate that there is no significant contribution from singlet biradical or zwitterionic resonance forms. The crystal structure of an ethyne-linked porphyrin dimer shows that the torsion angle between the porphyrin units is only about 3°, in keeping with crystallographic results on related compounds, but contrasting with the torsion angle of about 35° predicted by computational studies. The free-base quinoidal porphyrin monomers form tightly π-stacked layer structures, despite their curved geometries and bulky aryl substituents.

  10. Preparation of [123I]- and [125I]epidepride: a dopamine D-2 receptor antagonist radioligand

    International Nuclear Information System (INIS)

    Clanton, J.A.; Schmidt, D.E.; Ansari, M.S.; Manning, R.G.; Kessler, R.M.; Paulis, T. de; Vanderbilt Univ., Nashville, TN; Baldwin, R.M.

    1991-01-01

    (S)-(-)-N-[(1-ethyl-2-pyrrolidinyl)methyl]-5-[ 123 I] iodo-2,3-dimethoxybenzamide (TDP 517) (proposed generic name, [ 123 I]epidepride) is the iodine-123 substituted analogue of isoremoxipride (FLB 457), both of which are very potent dopamine D-2 antagonists (epidepride K D 0.024 nM). [ 123 I] Epidepride was radioiodinated in 60-70% radiochemical yields in 35 min from the corresponding 5-(tributyltin) derivative using Na 123 I with a specific radioactivity of 3000 Ci/mmol, and oxidized in situ with chloramine-T. The aryltin precursor was prepared from non-labelled epidepride by palladium-catalyzed stannylation using bis(tri-n-butyltin) in triethylamine. Alternatively, using no carrier-added Na 125 I as the radioisotope, [ 125 I] epidepride at 2000 Ci/mmol specific radioactivity was prepared in 86% radiochemical yield and 99% radiochemical purity after purification by reverse phase HPLC in ethanolic phosphate buffer. (author)

  11. Facile Synthesis of N-Tosyl Aza-Baylis-Hillman Adducts of Acrylamide via a Pd-Catalyzed Hydration of Nitrile to Amide

    International Nuclear Information System (INIS)

    Kim, Eun Sun; Kim, Yu Mi; Kim, Jae Nyoung

    2010-01-01

    We developed an efficient palladium-catalyzed two-step protocol for the synthesis of N-tosyl aza-Baylis-Hillman adducts of acrylamide. The method involved the preparation of the corresponding Baylis-Hillman adducts of acrylonitrile and the following Pd-catalyzed hydration of nitrile with acetaldoxime. The Baylis-Hillman reaction, which involves the coupling of activated vinyl compounds with electrophiles under the catalytic influence of a tertiary amine, gives rise to adducts, so called Baylis-Hillman adducts, with a new stereocenter and has proven to be a very useful carbon-carbon bond-forming method in the synthesis of highly functionalized molecules. As the activated vinyl compounds, various compounds have been used in the Baylis-Hillman reaction including acrylates, acrylonitrile, vinyl ketones, vinyl sulfones and acrylamides. However, among the activated vinyl compounds acrylamide has not been used much for the synthesis of the corresponding Baylis-Hillman adducts due to its sluggish reactivity

  12. Synthesis of heterocycles via transition-metal-catalyzed hydroarylation of alkynes.

    Science.gov (United States)

    Yamamoto, Yoshihiko

    2014-03-07

    Transition-metal (TM)-catalyzed hydroarylation reactions of alkynes have received much attention, because they enable the net insertion of alkyne C-C triple bonds into C-H bonds of aromatic precursors, resulting in regio- and stereo-selective formation of synthetically useful arylalkenes. Taking advantage of this feature, TM-catalyzed alkyne hydroarylations have been successfully used for the synthesis of heterocycles. TM-catalyzed alkyne hydroarylations can be classified into three major categories depending on the type of reaction and precursors involved: (1) palladium-catalyzed reductive Heck reactions of alkynes with aryl halides, (2) TM-catalyzed conjugate arylation reactions of activated alkynes with arylboronic acids, and (3) TM-catalyzed aromatic C-H alkenylations with alkynes. This review surveys heterocycle synthesis via TM-catalyzed hydroarylation of alkynes according to the above classification, with an emphasis on the scope and limitations, as well as the underlying mechanisms.

  13. Photoredox-Catalyzed Stereoselective Conversion of Alkynes into Tetrasubstituted Trifluoromethylated Alkenes.

    Science.gov (United States)

    Tomita, Ren; Koike, Takashi; Akita, Munetaka

    2015-10-26

    A regio- and stereoselective synthesis of trifluoromethylated alkenes bearing four different substituents has been developed. Stereocontrolled sulfonyloxytrifluoromethylation of unsymmetric internal alkynes with an electrophilic CF3 reagent, namely the triflate salt of the Yagupol'skii-Umemoto reagent, in the presence of an Ir photoredox catalyst under visible-light irradiation afforded trifluoromethylalkenyl triflates with well-predictable stereochemistry resulting from anti addition of the trifluoromethyl and triflate groups. Subsequent palladium-catalyzed cross-couplings led to tetrasubstituted trifluoromethylated alkenes in a highly stereoselective manner. The present method is the first example of a facile one-pot synthesis of tetrasubstituted trifluoromethylated alkenes from simple alkynes. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Synthesis and optical properties of new 5'-aryl-substituted 2,5-bis(3-decyl-2,2'-bithiophen-5-yl-1,3,4-oxadiazoles

    Directory of Open Access Journals (Sweden)

    Anastasia S. Kostyuchenko

    2017-02-01

    Full Text Available New photoluminescent donor–acceptor–donor (DAD molecules, namely 5'-aryl-substituted 2,5-bis(3-decyl-2,2'-bithiophen-5-yl-1,3,4-oxadiazoles were prepared by palladium-catalyzed coupling from readily available compounds such as ethyl 3-decyl-2,2'-bithiophene-5-carboxylate and aryl halides. The obtained compounds feature increasing bathochromic shifts in their emission spectra with increasing aryl-substituent size yielding blue to bluish-green emissions. At the same time, their absorption spectra are almost independent from the identity of the terminal substituent with λmax values ranging from 395 to 405 nm. The observed trends are perfectly predicted by quantum chemical DFT/TDDFT calculations carried out for these new molecules.

  15. Synthesis and characterization of deuterated polyethylene

    International Nuclear Information System (INIS)

    Jia Xianbin; Luo Xuan; Chang Guanjun; Du Kai; Zhang Lin; Xie Zhengwei; Li Xinjuan; Lu Zaijun

    2009-01-01

    Due to its remarkable isotope effects, excellent kinetic stability towards C-D bond break, high degree of deuteration, and being non-radioactive, deuterated polyethylene (d-PE) is widely used in many fields, such as in inertially confined fusion (ICF) as target material, in production of low loss plastic optical fibers, and in study of the compatibility of different polymers. For the necessary of ICF, the d-PE was synthesized by the anionic polymerization and palladium-catalyzed hydrogenation. Furthermore, by the method of FTIR, 1H NMR and GPC, the deuterated ratio and structure of d-PE have been characterized. The results show that the d-PE has the high deuterated ratio and molecular weight, narrow molecular-weight distribution, the polymer material fits the basic necessary of ICF. (authors)

  16. Synthesis of highly functionalized 2,2'-bipyridines by cyclocondensation of β-ketoenamides – scope and limitations

    Directory of Open Access Journals (Sweden)

    Paul Hommes

    2016-06-01

    Full Text Available The scope of a flexible route to unsymmetrically functionalized bipyridines is described. Starting from 1,3-diketones 1a–e, the corresponding β-ketoenamines 2a–e were converted into different β-ketoenamides 3a–g by N-acylation with 2-pyridinecarboxylic acid derivatives. These β-ketoenamides were treated with a mixture of TMSOTf and Hünig’s base to promote the cyclocondensation to 4-hydroxypyridine derivatives. Their immediate O-nonaflation employing nonafluorobutanesulfonyl fluoride provided the expected 4-nonafloxy-substituted bipyridine derivatives 5a–g in moderate to good overall yields. The bipyridyl nonaflates are excellent precursors for palladium-catalyzed reactions as demonstrated by representative Suzuki and Sonogashira couplings. Thus, a library of specifically substituted bipyridine derivatives was generated, showing the versatility of the simple 1,3-diketone-based approach to this important class of ligands.

  17. The synthesis of [[sup 2]H],[[sup 3]H], and [[sup 14]C]-labeled 8[beta]-[(methylthio)methyl]-6-propylergoline mesylate (pergolide mesylate), a potent, long-acting dopamine agonist

    Energy Technology Data Exchange (ETDEWEB)

    Wheeler, W.J.; Kau, D.L.K.; Bach, N.J. (Lilly (Eli) and Co., Indianapolis, IN (United States). Lilly Research Labs.)

    1990-03-01

    The [[sup 3]H]- and two[[sup 14]C]-isopomers of 8[beta]-[(methylthio)methyl]-6-propylergoline mesylate (pergolide mesylate) have been synthesized. The [[sup 3]H]-derivative was synthesized by the palladium catalyzed tritiation of the corresponding 6-allyl derivative. Reaction of 8[beta]-[(methylthio)methyl]-ergoline with 1-[[sup 14]C]-1-propyl bromide yielded pergolide labeled in the 6-propyl group. Alternatively, reaction of 8[beta]-mesyloxy-6-propylergoline with [[sup 14]C]-sodium cyanide, followed by base hydrolysis, yielded 8 [beta]-carboxy-6-propylergoline-[[sup 14]C], which was subsequently converted to pergolide mesylate radiolabeled in the 17-position via a four step sequence. (Author).

  18. NeoPHOX – a structurally tunable ligand system for asymmetric catalysis

    Directory of Open Access Journals (Sweden)

    Jaroslav Padevět

    2016-06-01

    Full Text Available A synthesis of new NeoPHOX ligands derived from serine or threonine has been developed. The central intermediate is a NeoPHOX derivative bearing a methoxycarbonyl group at the stereogenic center next to the oxazoline N atom. The addition of methylmagnesium chloride leads to a tertiary alcohol, which can be acylated or silylated to produce NeoPHOX ligands with different sterical demand. The new NeoPHOX ligands were tested in the iridium-catalyzed asymmetric hydrogenation and palladium-catalyzed allylic substitution. In both reactions high enantioselectivities were achieved, that were comparable to the enantioselectivities obtained with the up to now best NeoPHOX ligand derived from expensive tert-leucine.

  19. Rhodium-catalyzed C-H bond activation for the synthesis of quinonoid compounds: Significant Anti-Trypanosoma cruzi activities and electrochemical studies of functionalized quinones.

    Science.gov (United States)

    Jardim, Guilherme A M; Silva, Thaissa L; Goulart, Marilia O F; de Simone, Carlos A; Barbosa, Juliana M C; Salomão, Kelly; de Castro, Solange L; Bower, John F; da Silva Júnior, Eufrânio N

    2017-08-18

    Thirty four halogen and selenium-containing quinones, synthesized by rhodium-catalyzed C-H bond activation and palladium-catalyzed cross-coupling reactions, were evaluated against bloodstream trypomastigotes of T. cruzi. We have identified fifteen compounds with IC 50 /24 h values of less than 2 μM. Electrochemical studies on A-ring functionalized naphthoquinones were also performed aiming to correlate redox properties with trypanocidal activity. For instance, (E)-5-styryl-1,4-naphthoquinone 59 and 5,8-diiodo-1,4-naphthoquinone 3, which are around fifty fold more active than the standard drug benznidazole, are potential derivatives for further investigation. These compounds represent powerful new agents useful in Chagas disease therapy. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

  20. A computational mechanistic study of Pd(ii)-catalyzed γ-C(sp3)-H olefination/cyclization of amines: the roles of bicarbonate and ligand effect.

    Science.gov (United States)

    Liu, Jian-Biao; Tian, Ying-Ying; Zhang, Xin; Wang, Lu-Lin; Chen, De-Zhan

    2018-04-03

    The detailed mechanism of palladium-catalyzed γ-C(sp3)-H olefination/cyclization of triflyl-protected amines was investigated by density functional theory (DFT) calculations. The olefinated intermediate was initially formed in the first catalytic cycle involving ligand exchange, bicarbonate-assisted C(sp3)-H bond cleavage, alkene insertion and 'reductive β-hydride elimination'. The following syn-addition and reductive elimination furnish the aza-Wacker product. The first step of reductive elimination is the rate-determining step. The mechanism unveils the important roles of bicarbonate: aiding the C-H activation and abstracting the β-proton in the second step of reductive elimination. The parallel bridging mode in the metal-olefin intermediate facilitates the syn-addition, explaining the experimentally observed stereoselectivity. The effect of the monodentate pyridine-based ligands is also discussed.

  1. Synthesis of carbasugars from aldonolactones, part III - A study on the allylic substitution of (1R,5R,8R)- and (1R,5R,8S)-8-hydroxy-2-oxabicyclo[3.3.0]oct-6-en-3-one derivatives - Preparation of (1S,2R,3R)-9-[2-hydroxy-3-(2-hydroxyethyl)cyclopent-4-en-1-yl]-9H-adenine

    DEFF Research Database (Denmark)

    Johansen, Steen Karsk; Lundt, Inge

    2001-01-01

    The palladium-catalyzed substitution of acylated (1R,5R,8R)- and (1R,SR,8S)-8-hydroxy-2-oxabicyclo[3.3.0] ones has been studied using a number of C- and N-nucleophiles, In all cases, the exo derivatives (8R) were found to be more reactive than the corresponding endo derivatives (8S). The reaction...... with these nucleophiles. Additionally, Mitsunobu substitution of (1R,5R,8R)-8-hydroxy-2-oxabicyclo[3.3.0]oct-B-en-3-one (3) with 6-chloropurine, followed by reduction of the lactone moiety and treatment with Liquid ammonia, gave the carbocyclic nucleoside (1S,2R,3R)-9-[2-hydroxy-3-(2-hydroxyethyl)cyclopent-4-en-1-yl]-9H...

  2. Stabilizing Pentacene By Cyclopentannulation.

    Science.gov (United States)

    Bheemireddy, Sambasiva R; Ubaldo, Pamela C; Rose, Peter W; Finke, Aaron D; Zhuang, Junpeng; Wang, Lichang; Plunkett, Kyle N

    2015-12-21

    A new class of stabilized pentacene derivatives with externally fused five-membered rings are prepared by means of a key palladium-catalyzed cyclopentannulation step. The target compounds are synthesized by chemical manipulation of a partially saturated 6,13-dibromopentacene precursor that can be fully aromatized in a final step through a DDQ-mediated dehydrogenation reaction (DDQ=2,3-dichloro-5,6-dicyano-1,4-benzoquinone). The new 1,2,8,9-tetraaryldicyclopenta[fg,qr]pentacene derivatives have narrow energy gaps of circa 1.2 eV and behave as strong electron acceptors with lowest unoccupied molecular orbital energies between -3.81 and -3.90 eV. Photodegradation studies reveal the new compounds are more photostable than 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS-pentacene). © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Camphyl-based α-diimine palladium complexes: highly efficient precatalysts for direct arylation of thiazoles in open-air.

    Science.gov (United States)

    Chen, Fu-Min; Lu, Dong-Dong; Hu, Li-Qun; Huang, Ju; Liu, Feng-Shou

    2017-07-21

    Based on the strategy of the development of phosphine-free palladium-catalyzed direct C-H arylation, a series of camphyl-based α-diimine palladium complexes bearing sterically bulky substituents were synthesized and characterized. The palladium complexes were applied for the cross-coupling of thiazole derivatives with aryl bromides. The effect of the sterically bulky substituent on the N-aryl moiety as well as the reaction conditions was screened. Under the optimal protocols, a wide range of aryl bromides can be smoothly coupled with thiazoles in good to excellent yields in the presence of a low palladium loading of 0.2 mol% under open-air conditions.

  4. Bedford-type palladacycle catalyzed Miyaura-borylation of aryl halides with tetrahydroxydiboron in water

    KAUST Repository

    Zernickel, Anna

    2018-01-09

    A mild aqueous protocol for palladium catalyzed Miyaura borylation of aryl iodides, aryl bromides and aryl chlorides with tetrahydroxydiboron (BBA) as a borylating agent is developed. The developed methodology requires low catalyst loading of Bedford-type palladacycle catalyst (0.05 mol %) and works best under mild reaction conditions at 40 °C in short time of 6 hours in water. In addition, our studies show that for Miyaura borylation using BBA in aqueous condition, maintaining a neutral reaction pH is very important for reproducibility and higher yields of corresponding borylated products. Moreover, our protocol is applicable for a broad range of aryl halides, corresponding borylated products are obtained in excellent yields up to 93% with 29 examples demonstrating its broad utility and functional group tolerance.

  5. Synthesis and labelling of epidepride

    International Nuclear Information System (INIS)

    Yang Min; Pei Zhuguo; Hu Mingyang; Wang Bocheng; Zhou Xingqin

    2001-01-01

    S-(-)-N-[(1-ethyl-2-pyrrolidinyl) methyl]-5-iodo-2,3-dimethoxybenzamide (proposed generic name, epidepride) is a very potent dopamine D2 antagonist. It was synthesized by five steps from 3-methoxysalicylic acid. [ 131 I]epidepride was obtained in 97.3% radiochemical yields from the corresponding 5-(tributyltin) derivative using hydrogen peroxide as the oxidant. The aryltin precursor was prepared from non-labelled epidepride by palladium-catalyzed stannylene using bis (tri-n-butyltin) in triethylamine. [ 131 I] epidepride was stable under 4 degree C, and partition coefficient was 72.3 at pH 7.40. The biodistribution study in rats exhibited high localization in the striatum of the brain with the striatum/cerebellum ratio reaching 237/1 at 320 min postinjection. All these results suggest that [ 131 I] epidepride may be used widely as a useful dopamine D2 receptor imaging agent for SPECT

  6. Synthesis and in vivo evaluation of carborane gadolinium-DTPA complex as an MR imaging boron carrier

    International Nuclear Information System (INIS)

    Nakamura, H.; Fukuda, H.; Girald, F.

    2000-01-01

    A carborane containing Gd-DTPA (diethylenetriaminepentaacetate) complex 2 was synthesized using a palladium-catalyzed C-C bond forming reaction. The evaluation of the Gd-carborane complex 2 as a MR imaging and boron carrier agent was carried out in vivo by means of MRI, ICP-AES, and α-autoradiography. The MR imaging revealed that the carborane Gd-DTPA 2 was metabolized slower in the body in comparison with Gd-DTPA 1. The results of ICP-AES method indicated that compound 2 was incorporated into normal tissues and metabolized quickly, whereas it was not accumulated into tumor and brain tissue. The α-autoradiography showed that a high level of boron was obtained in the internal organs and in the necrosis of tumor tissue. (author)

  7. 26 CFR 1.125-4T - Permitted election changes (temporary).

    Science.gov (United States)

    2010-04-01

    ..., divorce, legal separation, or annulment; (ii) Number of dependents. Events that change an employee's... that causes an employee's dependent to satisfy or cease to satisfy the requirements for coverage due to... coverage. In the case of divorce, legal separation, annulment, or death of a spouse or dependent, a...

  8. Zinc mediated domino elimination-alkylation of methyl 5-iodopentofuranosides

    DEFF Research Database (Denmark)

    Hyldtoft, Lene; Poulsen, Carina Storm; Madsen, Robert

    1999-01-01

    5-Iodopentofuranosides are converted with zinc and allyl/propargyl bromide into dienes/enynes which are further used in carbohydrate annulation reactions.......5-Iodopentofuranosides are converted with zinc and allyl/propargyl bromide into dienes/enynes which are further used in carbohydrate annulation reactions....

  9. 77 FR 71687 - Federal Employees' Group Life Insurance Program: Court Orders Prior to July 22, 1998

    Science.gov (United States)

    2012-12-04

    ... regulations regarding the effect of any court decree of divorce, annulment, or legal separation, or any court- approved property settlement agreement incident to any court decree of divorce, annulment, or legal... court decision and adds little substantive interpretation of the law. For the foregoing reasons, OPM...

  10. 38 CFR 3.660 - Dependency, income and estate.

    Science.gov (United States)

    2010-07-01

    ..., divorce or death, or because of an increase in income, which increase could not reasonably have been..., annulment, divorce, or death, the award shall be reduced or discontinued effective the last day of the..., due to marriage, annulment, divorce or death, the reduction or discontinuance shall be effective the...

  11. Total Syntheses of Polycyclic Polyprenylated Acylphloroglucinol Natural Products and Analogs Utilizing Alkylative Dearomatizations and Cationic Cyclizations

    Science.gov (United States)

    Boyce, Jonathan H.

    Polycyclic polyprenylated acylphloroglucinols (PPAPs) are structurally complex natural products with promising biological activities. These compounds have interesting anticancer and anti-HIV properties as well as other biological activities making them highly attractive synthetic targets. We report a stereodivergent, asymmetric total synthesis of (-)-clusianone in six steps from commercial materials. We have implemented a challenging cationic cyclization forging a bond between two sterically encumbered quaternary carbon atoms. Mechanistic studies point to the unique ability of formic acid to mediate the cyclization forming the clusianone framework. We also present a biosynthesis-inspired, diversity-oriented synthesis approach for rapid construction of PPAP analogs via palladium-catalyzed dearomative conjunctive allylic alkylation (DCAA). These efficient palladium-catalyzed protocols construct the [3.3.1]-bicyclic PPAP core in a single step from their stable aromatic precursors. The first syntheses of 13,14-didehydroxyisogarcinol and garcimultiflorone A stereoisomers are reported in six steps from a commercially available phloroglucinol. Lewis acid-controlled, diastereoselective cationic oxycyclizations enabled asymmetric syntheses of (-)-6-epi-13,14-didehydroxyisogarcinol and (+)-30-epi-13,14-didehydroxyisogarcinol. A similar strategy enabled production of the meso-derived isomers (+/-)-6,30- epi-13,14-didehydroxyisogarcinol and (+/-)-6,30-epi -garcmultiflorone A. A convenient strategy for gram scale synthesis of these stereoisomers was developed utilizing diastereomer separation at a later stage in the synthesis that minimized the number of necessary synthetic operations to access all possible stereoisomers. Finally, we report cationic rearrangements of dearomatized acylphloroglucinols leading to the formation of unprecedented PPAP scaffolds. A novel type A [3.3.1]-bicyclic PPAP was produced as a major product and the structure confirmed by X-ray crystallographic

  12. Réttaráhrif annmarka á framkvæmd kosninga með hliðsjón af úrlausnum Hæstaréttar Íslands

    DEFF Research Database (Denmark)

    Baldvinsson, Gunnar Pall; Solnes, Valgerdur

    2014-01-01

    The Icelandic judicial system has dealt with questions regarding the validity of election. Most recently the Supreme Court of Iceland upheld the validity of the presedential elections of 2012 in its Decisions of 25 July 2012 and annulled the election of members for a constitutional assembly of 20......, i.e. the right to vote by secret ballot....... regarding annulment of elections in the Act on Parliamentary Elections in the Act on Municipal Elections contain the same rule, despite the provisions´ nuanced wording. The rule of annulment instrinsically states that elections are subject to annulment should any defects in the candidacy or election arise...... of the Supreme Court, where a general measure has been a decisive factor for the annulment of elections, reveals that said rulings contain an important convergence. The rulings have all included circumstances where an electoral defect has been subject to an essential right protected by the Icelandic Constitution...

  13. Synthesis of Unsymmetrical Annulated 2,2’-Bipyridine Analogues with Attached Cycloalkene and Piperidine Rings via Sequential Diels-Alder Reaction of 5,5’-bi-1,2,4-triazinesâ€

    Directory of Open Access Journals (Sweden)

    D. Branowska

    2005-12-01

    Full Text Available Synthesis of bisfunctionalized unsymmetrical 2,2’-bipyridines 8 or their sulfonyl derivatives 12a,b are described. They were prepared via the Diels-Alder reaction of 1-methyl-4-pyrrolidin-1-yl-1,2,3,6-tetrahydropyridine (6 with 3,3’-bis(methyl- sulfanyl-5,5’-bi-1,2,4-triazine (1. The reaction leads to the single cycloaddition product 7 which undergoes Diels-Alder reaction with cyclic enamines 2a,b to give unsymmetrical 2,2’-bipyridine derivatives 8, consisting of the two different heterocyclic units: cycloalkeno[c]pyridine and 2,6-naphthyridine.

  14. (ICSID) ADDITIONAL FACILITY IN INTERNA

    African Journals Online (AJOL)

    Fr. Ikenga

    ... which is adopted by Article 5 of the Additional Facility Rules to guide the ... B, Barrister at Law, e-mail: kcezeibe@yahoo.com; Phone 08033950631 and .... revision and annulment which are internally available under the Washington ...

  15. Soluble Polymer-supported Synthesis of Indoles via Palladium-mediat -ed Heteroannulation of Terminal Alkynes with o-Iodoanilines

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    A soluble polymer-supported synthesis of indoles via palladium-mediated hetero- annulation of terminal alkynes with o-iodoanilines has been described. The protocol provides a useful tool for constructing combinatorial indole libraries.

  16. A HIGHLY STEREOSELECTIVE, NOVEL COUPLING REACTION BETWEEN ALKYNES WITH ALDEHYDES. (R828129)

    Science.gov (United States)

    In the presence of indium triflate or gallium chloride, a novel coupling between internal alkynes and aldehydes occurred to give unsaturated ketones and [4+1] annulation products. Graphical Abstrac...

  17. On a Linear Equation Arising in Isometric Embedding of Torus-like Surface

    Institute of Scientific and Technical Information of China (English)

    Chunhe LI

    2009-01-01

    The solvability of a linear equation and the regularity of the solution are discussed.The equation is arising in a geometric problem which is concerned with the realization of Alexandroff's positive annul in R3.

  18. Het relativiteitsvereiste van artikel 8:69a Awb : de stand van zaken

    NARCIS (Netherlands)

    van der Veen, G.A.

    2015-01-01

    The principle of relativity is a new principle in dutch administrative law. It restricts the annulment powers of the administrative judge. The article deals with the concept of the principle and the appearance in case law of the administrative judge

  19. 22 CFR 20.9 - Application procedure.

    Science.gov (United States)

    2010-04-01

    ... by June 22, 1990 or, if an exception is made for compelling cause to this deadline, within 60 days... divorce or annulment that establish eligibility and fully identify the Foreign Service employee or former...

  20. 5 CFR 890.1105 - Initial election of temporary continuation of coverage; application time limitations and...

    Science.gov (United States)

    2010-01-01

    ... (ii) The date of the divorce or annulment. (e) If an individual who is eligible for temporary... determines that an eligible individual was unable, for cause beyond his or her control, to elect temporary...

  1. Antiaromatic bisindeno-[n]thienoacenes with small singlet biradical characters: Syntheses, structures and chain length dependent physical properties

    KAUST Repository

    Shi, Xueliang; Burrezo, Paula Mayorga; Lee, Sangsu; Zhang, Wenhua; Zheng, Bin; Dai, Gaole; Chang, Jingjing; Lõ pez Navarrete, Juan Teodomiro; Huang, Kuo-Wei; Kim, Dongho; Casado, Juan; Chi, Chunyan

    2014-01-01

    showing promising applications for organic electronics, photonics and spintronics. In this work, we designed and synthesized a new type of hybrid system, the so-called bisindeno-[n]thienoacenes (n = 1-4), by annulation of quinoidal fused α

  2. Interest of pelvimetry by multi detectors computed tomography (M.D.C.T.) 40 pins, reduction of the delivered dose

    International Nuclear Information System (INIS)

    Thibaut, C.; Marie-Anne, O.; Douws, C.; Grenier, N.; Chateil, J.F.

    2006-01-01

    This new procedure has allowed to improve the quality of measurement accuracy, annuls the difficulties of realizations of the conventional pictures and reduces in a considerable way the dose delivered to the patient and to the baby. (N.C.)

  3. 5 CFR 843.305 - Reinstatement.

    Science.gov (United States)

    2010-01-01

    ... annuity is reinstated on the day of the termination of the remarriage by death, annulment, or divorce if... reason of the remarriage; and (2) Any lump sum paid on termination of the annuity is repaid (in a single...

  4. 20 CFR 219.35 - Evidence that a marriage has ended.

    Science.gov (United States)

    2010-04-01

    ... divorce or annulment; or (2) Evidence of the death (See § 219.23) of a party to the marriage. (b) Other..., the claimant must explain the reason therefor and submit other convincing evidence that the marriage...

  5. Reversal of Liver Fibrosis in Chronic Murine Schistosomiasis ...

    African Journals Online (AJOL)

    In schistosomiasis, healing of parasite egg- induced liver ... greater in liver than in other tissues. It has been reported that ..... biology, diseases, and potentials for therapy. Annul Rev Biochem ... regeneration in cirrhotic rats. J Hepatol, 2002;.

  6. Cephalobellus lobulata n. sp. (Oxyurida:Thelastomatidae a parasite of Neocurtilla claraziana Saussure (Orthoptera: Gryllotalpidae from Argentina

    Directory of Open Access Journals (Sweden)

    Camino Nora B

    2000-01-01

    Full Text Available Cephalobellus lobulata n. sp. (Oxyurida: Thelastomatidae a parasite of the mole cricket Neocurtilla claraziana Saussure (Orthoptera: Gryllotalpidae found in Argentina is described and illustrated. It is characterized by a short buccal cavity armed with three teeth, a striated cuticle with the first annule wide with four lobes and the second annule divided in twelve lobes. The male have three pairs of preanal papillae and two pairs of postanal papillae.

  7. Cephalobellus lobulata n. sp. (Oxyurida:Thelastomatidae) A parasite of Neocurtilla claraziana Saussure (Orthoptera: gryllotalpidae) from Argentina.

    Science.gov (United States)

    Camino, N B; Reboredo, G R

    2000-01-01

    Cephalobellus lobulata n. sp. (Oxyurida: Thelastomatidae) a parasite of the mole cricket Neocurtilla claraziana Saussure (Orthoptera: Gryllotalpidae) found in Argentina is described and illustrated. It is characterized by a short buccal cavity armed with three teeth, a striated cuticle with the first annule wide with four lobes and the second annule divided in twelve lobes. The male have three pairs of preanal papillae and two pairs of postanal papillae.

  8. Synthesis and properties of functionalized 4 nm scale molecular wires with thiolated termini for self-assembly onto metal surfaces.

    Science.gov (United States)

    Wang, Changsheng; Bryce, Martin R; Gigon, Joanna; Ashwell, Geoffrey J; Grace, Iain; Lambert, Colin J

    2008-07-04

    We report the synthesis of new oligo(aryleneethynylene) molecular wires of ca. 4 nm length scale by palladium-catalyzed Sonogashira cross-coupling methodology. Key structural features are the presence of electron donor 9-(1,3-dithiol-2-ylidene)fluorene (compounds 13 and 14) and electron acceptor 9-[di(4-pyridyl)methylene]fluorene units (compound 16) at the core of the molecules. Terminal thiolate substituents are protected as cyanoethylsulfanyl (13 and 16) or thioacetate derivatives (14). The molecules display well-defined redox processes in solution electrochemical studies. The optical properties in solution are similar to those of the fluorenone analog 6: the strongest absorptions for 6, 13 and 16 are in the region lambda(max) = 387-393 nm, with 13 showing an additional shoulder at 415 nm which is not present for 6 and 16; this shoulder is assigned to a HOMO-LUMO transition from the dithiole to the fluorene unit. Molecules 6, 13, 14 and 16 form self-assembled monolayers on gold substrates which exhibit essentially symmetrical current-voltage (I-V) characteristics when contacted by a gold scanning tunelling microscope (STM) tip. The effects of the chemical modifications at the central unit of 6, 14 and 16 on the HOMO-LUMO levels and electron transport through the molecules in vacuum have been computed by an ab initio approach.

  9. Efficient synthetic protocols in glycerol under heterogeneous catalysis.

    Science.gov (United States)

    Cravotto, Giancarlo; Orio, Laura; Gaudino, Emanuela Calcio; Martina, Katia; Tavor, Dorith; Wolfson, Adi

    2011-08-22

    The massive increase in glycerol production from the transesterification of vegetable oils has stimulated a large effort to find novel uses for this compound. Hence, the use of glycerol as a solvent for organic synthesis has drawn particular interest. Drawbacks of this green and renewable solvent are a low solubility of highly hydrophobic molecules and a high viscosity, which often requires the use of a fluidifying co-solvent. These limitations can be easily overcome by performing reactions under high-intensity ultrasound and microwaves in a stand-alone or combined manner. These non-conventional techniques facilitate and widen the use of glycerol as a solvent in organic synthesis. Glycerol allows excellent acoustic cavitation even at high temperatures (70-100 °C), which is otherwise negligible in water. Herein, we describe three different types of applications: 1) the catalytic transfer hydrogenation of benzaldehyde to benzyl alcohol in which glycerol plays the dual role of the solvent and hydrogen donor; 2) the palladium-catalyzed Suzuki cross-coupling; and (3) the Barbier reaction. In all cases glycerol proved to be a greener, less expensive, and safer alternative to the classic volatile organic solvents. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Enantioselective functionalization of allylic C-H bonds following a strategy of functionalization and diversification.

    Science.gov (United States)

    Sharma, Ankit; Hartwig, John F

    2013-11-27

    We report the enantioselective functionalization of allylic C-H bonds in terminal alkenes by a strategy involving the installation of a temporary functional group at the terminal carbon atom by C-H bond functionalization, followed by the catalytic diversification of this intermediate with a broad scope of reagents. The method consists of a one-pot sequence of palladium-catalyzed allylic C-H bond oxidation under neutral conditions to form linear allyl benzoates, followed by iridium-catalyzed allylic substitution. This overall transformation forms a variety of chiral products containing a new C-N, C-O, C-S, or C-C bond at the allylic position in good yield with a high branched-to-linear selectivity and excellent enantioselectivity (ee ≤97%). The broad scope of the overall process results from separating the oxidation and functionalization steps; by doing so, the scope of nucleophile encompasses those sensitive to direct oxidative functionalization. The high enantioselectivity of the overall process is achieved by developing an allylic oxidation that occurs without acid to form the linear isomer with high selectivity. These allylic functionalization processes are amenable to an iterative sequence leading to (1,n)-functionalized products with catalyst-controlled diastereo- and enantioselectivity. The utility of the method in the synthesis of biologically active molecules has been demonstrated.

  11. Bioorthogonal Diversification of Peptides through Selective Ruthenium(II)-Catalyzed C-H Activation.

    Science.gov (United States)

    Schischko, Alexandra; Ren, Hongjun; Kaplaneris, Nikolaos; Ackermann, Lutz

    2017-02-01

    Methods for the chemoselective modification of amino acids and peptides are powerful techniques in biomolecular chemistry. Among other applications, they enable the total synthesis of artificial peptides. In recent years, significant momentum has been gained by exploiting palladium-catalyzed cross-coupling for peptide modification. Despite major advances, the prefunctionalization elements on the coupling partners translate into undesired byproduct formation and lengthy synthetic operations. In sharp contrast, we herein illustrate the unprecedented use of versatile ruthenium(II)carboxylate catalysis for the step-economical late-stage diversification of α- and β-amino acids, as well as peptides, through chemo-selective C-H arylation under racemization-free reaction conditions. The ligand-accelerated C-H activation strategy proved water-tolerant and set the stage for direct fluorescence labelling as well as various modes of peptide ligation with excellent levels of positional selectivity in a bioorthogonal fashion. The synthetic utility of our approach is further demonstrated by twofold C-H arylations for the complexity-increasing assembly of artificial peptides within a multicatalytic C-H activation manifold. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Influence of hydroxylamine conformation on stereocontrol in Pd-catalyzed isoxazolidine-forming reactions.

    Science.gov (United States)

    Lemen, Georgia S; Giampietro, Natalie C; Hay, Michael B; Wolfe, John P

    2009-03-20

    Palladium-catalyzed carboamination reactions between N-Boc-O-(but-3-enyl)hydroxylamine derivatives and aryl or alkenyl bromides afford cis-3,5- and trans-4,5-disubstituted isoxazolidines in good yield with up to >20:1 dr. The diastereoselectivity observed in the formation of cis-3,5-disubstituted isoxazolidines is superior to selectivities typically obtained in other transformations, such as 1,3-dipolar cycloaddition reactions, that provide these products. In addition, the stereocontrol in the C-N bond-forming Pd-catalyzed carboamination reactions of N-Boc-O-(but-3-enyl)hydroxylamines is significantly higher than that of related C-O bond-forming carboetherification reactions of N-benzyl-N-(but-3-enyl)hydroxylamine derivatives. This is likely due to a stereoelectronic preference for cyclization via transition states in which the Boc group is placed in a perpendicular orientation relative to the plane of the developing ring, which derives from the conformational equilibria of substituted hydroxylamines.

  13. N-O chemistry for antibiotics: discovery of N-alkyl-N-(pyridin-2-yl)hydroxylamine scaffolds as selective antibacterial agents using nitroso Diels-Alder and ene chemistry.

    Science.gov (United States)

    Wencewicz, Timothy A; Yang, Baiyuan; Rudloff, James R; Oliver, Allen G; Miller, Marvin J

    2011-10-13

    The discovery, syntheses, and structure-activity relationships (SAR) of a new family of heterocyclic antibacterial compounds based on N-alkyl-N-(pyridin-2-yl)hydroxylamine scaffolds are described. A structurally diverse library of ∼100 heterocyclic molecules generated from Lewis acid-mediated nucleophilic ring-opening reactions with nitroso Diels-Alder cycloadducts and nitroso ene reactions with substituted alkenes was evaluated in whole cell antibacterial assays. Compounds containing the N-alkyl-N-(pyridin-2-yl)hydroxylamine structure demonstrated selective and potent antibacterial activity against the Gram-positive bacterium Micrococcus luteus ATCC 10240 (MIC(90) = 2.0 μM or 0.41 μg/mL) and moderate activity against other Gram-positive strains including antibiotic resistant strains of Staphylococcus aureus (MRSA) and Enterococcus faecalis (VRE). A new synthetic route to the active core was developed using palladium-catalyzed Buchwald-Hartwig amination reactions of N-alkyl-O-(4-methoxybenzyl)hydroxylamines with 2-halo-pyridines that facilitated SAR studies and revealed the simplest active structural fragment. This work shows the value of using a combination of diversity-oriented synthesis (DOS) and parallel synthesis for identifying new antibacterial scaffolds.

  14. Excess Sodium Tetraphenylborate and Intermediates Decomposition Studies

    International Nuclear Information System (INIS)

    Barnes, M.J.; Peterson, R.A.

    1998-04-01

    The stability of excess amounts of sodium tetraphenylborate (NaTPB) in the In-Tank Precipitation (ITP) facility depends on a number of variables. Concentration of palladium, initial benzene, and sodium ion as well as temperature provide the best opportunities for controlling the decomposition rate. This study examined the influence of these four variables on the reactivity of palladium-catalyzed sodium tetraphenylborate decomposition. Also, single effects tests investigated the reactivity of simulants with continuous stirring and nitrogen ventilation, with very high benzene concentrations, under washed sodium concentrations, with very high palladium concentrations, and with minimal quantities of excess NaTPB. These tests showed the following.The testing demonstrates that current facility configuration does not provide assured safety of operations relative to the hazards of benzene (in particular to maintain the tank headspace below 60 percent of the lower flammability limit (lfl) for benzene generation rates of greater than 7 mg/(L.h)) from possible accelerated reaction of excess NaTPB. Current maximal operating temperatures of 40 degrees C and the lack of protection against palladium entering Tank 48H provide insufficient protection against the onset of the reaction. Similarly, control of the amount of excess NaTPB, purification of the organic, or limiting the benzene content of the slurry (via stirring) and ionic strength of the waste mixture prove inadequate to assure safe operation

  15. Excess Sodium Tetraphenylborate and Intermediates Decomposition Studies

    Energy Technology Data Exchange (ETDEWEB)

    Barnes, M.J. [Westinghouse Savannah River Company, AIKEN, SC (United States); Peterson , R.A.

    1998-04-01

    The stability of excess amounts of sodium tetraphenylborate (NaTPB) in the In-Tank Precipitation (ITP) facility depends on a number of variables. Concentration of palladium, initial benzene, and sodium ion as well as temperature provide the best opportunities for controlling the decomposition rate. This study examined the influence of these four variables on the reactivity of palladium-catalyzed sodium tetraphenylborate decomposition. Also, single effects tests investigated the reactivity of simulants with continuous stirring and nitrogen ventilation, with very high benzene concentrations, under washed sodium concentrations, with very high palladium concentrations, and with minimal quantities of excess NaTPB. These tests showed the following.The testing demonstrates that current facility configuration does not provide assured safety of operations relative to the hazards of benzene (in particular to maintain the tank headspace below 60 percent of the lower flammability limit (lfl) for benzene generation rates of greater than 7 mg/(L.h)) from possible accelerated reaction of excess NaTPB. Current maximal operating temperatures of 40 degrees C and the lack of protection against palladium entering Tank 48H provide insufficient protection against the onset of the reaction. Similarly, control of the amount of excess NaTPB, purification of the organic, or limiting the benzene content of the slurry (via stirring) and ionic strength of the waste mixture prove inadequate to assure safe operation.

  16. Tetrahydrofuran Calpha-tetrasubstituted amino acids: two consecutive beta-turns in a crystalline linear tripeptide.

    Science.gov (United States)

    Maity, Prantik; Zabel, Manfred; König, Burkhard

    2007-10-12

    The synthesis of tetrahydrofuran Calpha-tetrasubstituted amino acids (TAAs) and their effect on the conformation in small peptides are reported. The synthesis starts from the protein amino acid methionine, which is protected at the C and N terminus and converted into the corresponding sulfonium salt by alkylation. Simple base treatment in the presence of an aryl aldehyde leads to the formation of tetrahydrofuran tetrasubstituted Calpha-amino acids in a highly diastereoselective (trans/cis ratio up to 97:3) reaction with moderate to good yields (35-78%) depending on the aldehyde used. Palladium-catalyzed coupling reactions allow a subsequent further functionalization of the TAA. The R,S,S-TAA-Ala dipeptide amide adopts a beta-turn type I conformation, whereas its S,R,S isomer does not. The R,S,S-Gly-TAA-Ala tripeptide amide shows in the solid state and in solution a conformation of two consecutive beta-turn type III structures, stabilized by i+3-->i intramolecular hydrogen bonds.

  17. Alternating copolymerization of fluoroalkenes with carbon monoxide.

    Science.gov (United States)

    Fujita, Tomoyuki; Nakano, Koji; Yamashita, Makoto; Nozaki, Kyoko

    2006-02-15

    The palladium-catalyzed alternating copolymerization of fluoroalkenes, represented as CH(2)=CH-CH(2)-C(n)F(2n+1), with CO was performed using (R,S)-BINAPHOS (2e) as a ligand. The CH(2)-C(n)F(2n+1) group is the most electronegative substituent ever reported for the copolymerization (Taft's sigma value of 0.90 for CH(2)CF(3)). The copolymer obtained from CH(2)=CH-CH(2)-C(8)F(17) (1a) existed as a mixture of polyspiroketal and polyketone, while that from CH(2)=CH-CH(2)-C(4)F(9) (1b) was a pure polyspiroketal, as was revealed by infrared and (13)C-CP/MAS NMR spectroscopies. The terminal structure of the polymer from 1b was confirmed by MALDI-TOF MS spectrometry. Detailed NMR studies suggested that the much higher reactivity with (R,S)-BINAPHOS (2e) than that with the conventional ligand DPPP (2a) can be attributed to the unique 1,2-insertion of the fluoroalkene into acylpalladium species. The existence of an electronegative substituent on the alpha-carbon of the palladium center is successfully avoided in the 1,2-insertion mechanism.

  18. Synthesis of carboranes containing azulene framework and in vitro evaluation as boron carriers

    International Nuclear Information System (INIS)

    Nakamura, Hiroyuki; Sekido, Masaru; Yamamoto, Yoshinori

    1998-01-01

    3-(o-Carboranylhydroxymethyl)-7-isopropylazulene sodium carboxylate 1 and 3-(o-carboranylmethyl)-7-isopropylazulene sodium sulfonate 2 were synthesized from the palladium catalyzed addition reaction of 1-carboranyltributylstannane 4 to azulene-aldehydes (3 and 9). Although the water solubility of 1 was of the order of 10 -6 M, that of 2 was of the order of 10 -3 M and was enough for clinical use. The cytotoxicity of 1 (IC 50 ) toward B-16 melanoma cells was of the order of 10 -5 M, whereas that of 2 was of the order of 10 -4 M. This value was close to that of BPA (∼9 x 10 -3 M) which is utilized for clinical use. The boron uptake by B-16 cells was 0.17 μgB/10 6 cells for 1 and 0.25 μgB/10 6 cells for 2. It is clear that compound 2 is accumulated into B-16 melanoma cells with significantly high level although it is highly water soluble and its cytotoxicity is significantly low. (author)

  19. Microwave-assisted intramolecular dehydrogenative Diels-Alder reactions for the synthesis of functionalized naphthalenes/solvatochromic dyes.

    Science.gov (United States)

    Kocsis, Laura S; Benedetti, Erica; Brummond, Kay M

    2013-04-01

    Functionalized naphthalenes have applications in a variety of research fields ranging from the synthesis of natural or biologically active molecules to the preparation of new organic dyes. Although numerous strategies have been reported to access naphthalene scaffolds, many procedures still present limitations in terms of incorporating functionality, which in turn narrows the range of available substrates. The development of versatile methods for direct access to substituted naphthalenes is therefore highly desirable. The Diels-Alder (DA) cycloaddition reaction is a powerful and attractive method for the formation of saturated and unsaturated ring systems from readily available starting materials. A new microwave-assisted intramolecular dehydrogenative DA reaction of styrenyl derivatives described herein generates a variety of functionalized cyclopenta[b]naphthalenes that could not be prepared using existing synthetic methods. When compared to conventional heating, microwave irradiation accelerates reaction rates, enhances yields, and limits the formation of undesired byproducts. The utility of this protocol is further demonstrated by the conversion of a DA cycloadduct into a novel solvatochromic fluorescent dye via a Buchwald-Hartwig palladium-catalyzed cross-coupling reaction. Fluorescence spectroscopy, as an informative and sensitive analytical technique, plays a key role in research fields including environmental science, medicine, pharmacology, and cellular biology. Access to a variety of new organic fluorophores provided by the microwave-assisted dehydrogenative DA reaction allows for further advancement in these fields.

  20. Synthesis and photophysical properties of a series of cyclopenta[b]naphthalene solvatochromic fluorophores.

    Science.gov (United States)

    Benedetti, Erica; Kocsis, Laura S; Brummond, Kay M

    2012-08-01

    The synthesis and photophysical properties of a series of naphthalene-containing solvatochromic fluorophores are described within. These novel fluorophores are prepared using a microwave-assisted dehydrogenative Diels-Alder reaction of styrene, followed by a palladium-catalyzed cross coupling reaction to install an electron donating amine group. The new fluorophores are structurally related to Prodan. Photophysical properties of the new fluorophores were studied and intriguing solvatochromic behavior was observed. For most of these fluorophores, high quantum yields (60-99%) were observed in methylene chloride in addition to large Stokes shifts (95-226 nm) in this same solvent. As the solvent polarity increased, so did the observed Stokes shift with one derivative displaying a Stokes shift of ~300 nm in ethanol. All fluorophore emission maxima, and nearly all absorption maxima were significantly red-shifted when compared to Prodan. Shifting the absorption and emission maxima of a fluorophore into the visible region increases its utility in biological applications. Moreover, the cyclopentane portion of the fluorophore structure provides an attachment point for biomolecules that will minimize disruptions of the photophysical properties.

  1. An improved synthesis of [125I]N-(diethylaminoethyl)-4-iodobenzamide: a potential ligand for imaging malignant melanoma

    International Nuclear Information System (INIS)

    John, C.S.; Reba, R.C.; Varma, V.M.; McAfee, J.G.; Saga, T.; Kinuya, S.; Le, N.; Jeong, J.M.; Paik, C.H.

    1993-01-01

    To improve the radiolabeling yield and the specific activity of [ 125 I]N-(2-diethylaminoethyl)-4-iodobenzamide(DAB), the aryltributyltin precursor was synthesized from the N-(2-diethylaminoethyl)-4-bromobenzamide derivative by palladium catalyzed stannylation using bis(tributyltin). The radiolabeled product, [ 125 I]DAB, was obtained by an iododestannylation reaction in high radiochemical yields (85-94%, radiochemical purity, > 98%) using chloramine-T as an oxidizing agent. The specific activity was greater than 1600 Ci/mmol. The biodistribution studies in nude mice implanted with human malignant melanoma xenograft showed a good tumor uptake (6.14% ID/g at 1 h, 2.81% ID/g at 6 h and 0.42% ID/g at 24 h) of [ 125 I]DAB. Unfortunately, a high uptake in the non-target organs, such as liver and lung was found. At 1 h post-injection the activity level in liver and lung was 11.76 and 7.58% ID/g, respectively. A slow clearance of activity from liver and lung was observed at 6 h (3.43 and 0.49% ID/g). These results demonstrate that iodinated IDAB is a potential radiopharmaceutical for the management of patients with malignant melanoma. (Author)

  2. Production of Plant Phthalate and its Hydrogenated Derivative from Bio-Based Platform Chemicals.

    Science.gov (United States)

    Lu, Rui; Lu, Fang; Si, Xiaoqin; Jiang, Huifang; Huang, Qianqian; Yu, Weiqiang; Kong, Xiangtao; Xu, Jie

    2018-04-06

    Direct transformation of bio-based platform chemicals into aromatic dicarboxylic acids and their derivatives, which are widely used for the manufacture of polymers, is of significant importance for the sustainable development of the plastics industry. However, limited successful chemical processes have been reported. This study concerns a sustainable route for the production of phthalate and its hydrogenated derivative from bio-based malic acid and erythritol. The key Diels-Alder reaction is applied to build a substituted cyclohexene structure. The dehydration reaction of malic acid affords fumaric acid with 96.6 % yield, which could be used as the dienophile, and 1,3-butadiene generated in situ through erythritol deoxydehydration serves as the diene. Starting from erythritol and dibutyl fumarate, a 74.3 % yield of dibutyl trans-4-cyclohexene-1,2-dicarboxylate is obtained. The palladium-catalyzed dehydrogenation of the cycloadduct gives a 77.8 % yield of dibutyl phthalate. Dibutyl trans-cyclohexane-1,2-dicarboxylate could be formed in nearly 100 % yield under mild conditions by hydrogenation of the cycloadduct. Furthermore, fumaric acid and fumarate, with trans configurations, were found to be better dienophiles for this Diels-Alder reaction than maleic acid and maleate, with cis configuration, based on the experimental and computational results. This new route will pave the way for the production of environmental friendly plastic materials from plants. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Enantiopure N-Acyldihydropyridones as Synthetic Intermediates: Asymmetric Synthesis of (-)-Septicine and (-)-Tylophorine.

    Science.gov (United States)

    Comins, Daniel L.; Chen, Xinghai; Morgan, Lawrence A.

    1997-10-17

    A concise asymmetric synthesis of (-)-septicine (1) and (-)-tylophorine (2) was accomplished with a high degree of stereocontrol in eight and nine steps, respectively. Addition of 4-(1-butenyl)magnesium bromide to 1-acylpyridinium salt 3, prepared in situ from 4-methoxy-3-(triisopropylsilyl)pyridine and the chloroformate of (-)-trans-2-(alpha-cumyl)cyclohexanol, gave a 91% yield of diastereomerically pure dihydropyridone 7. Oxidative cleavage of 7 and subsequent reduction provided alcohol 6 in 81% yield. Conversion of 6 to the chloride followed by treatment with sodium methoxide gave indolizidinone 9 in high yield. Bromination and conjugate reduction of 9 with L-Selectride, and trapping the intermediate enolate with N-(5-chloro-2-pyridyl)triflimide, provided bromovinyl triflate 11. Palladium-catalyzed cross-coupling of excess (3,4-dimethoxyphenyl)zinc bromide and 11 gave (-)-septicine (1). On the basis of this synthesis, (-)-1 was assigned the Rconfiguration. Reaction of 1 with vanadium(V) trifluoride oxide in TFA/CH(2)Cl(2) effected oxidative coupling to give a 68% yield of (-)-tylophorine (2).

  4. Practical synthesis of aryl-2-methyl-3-butyn-2-ols from aryl bromides via conventional and decarboxylative copper-free Sonogashira coupling reactions

    Directory of Open Access Journals (Sweden)

    Andrea Caporale

    2014-02-01

    Full Text Available Two efficient protocols for the palladium-catalyzed synthesis of aryl-2-methyl-3-butyn-2-ols from aryl bromides in the absence of copper were developed. A simple catalytic system consisting of Pd(OAc2 and P(p-tol3 using DBU as the base and THF as the solvent was found to be highly effective for the coupling reaction of 2-methyl-3-butyn-2-ol (4 with a wide range of aryl bromides in good to excellent yields. Analogously, the synthesis of aryl-2-methyl-3-butyn-2-ols was performed also through the decarboxylative coupling reaction of 4-hydroxy-4-methyl-2-pentynoic acid with aryl bromides, using a catalyst containing Pd(OAc2 in combination with SPhos or XPhos in the presence of tetra-n-butylammonium fluoride (TBAF as the base and THF as the solvent. Therefore, new efficient approaches to the synthesis of terminal acetylenes from widely available aryl bromides rather than expensive iodides and using 4 or propiolic acid rather than TMS-acetylene as inexpensive alkyne sources are described.

  5. Synthesis and characterisation of nitrogen-containing poly heterocyclic molecules for the complexation of polluting metal cations; Synthese et caracterisation de molecules polyheterocycliques azotees pour la complexation de cations metalliques polluants

    Energy Technology Data Exchange (ETDEWEB)

    Leconte, N

    2007-12-15

    The recovery of actinides(III) from the mixture actinides(III)/lanthanides(III) is a great deal of the nuclear waste management. Experiences have shown that derivatives of 2,6- bis(1,2,4-triazine-3-yl)pyridine (BTP) are able to extract selectively actinides(III) from lanthanides(III). But the properties of these molecules need to be reinforced to exhibit best extraction performances and to resist to the harsh conditions of the extracting processes. Originally functionalized ligands were synthesized and tested in a radioactive medium. In a second part, this work focuses on the control and the detection of actinides(III). This could be done thanks to the use of a chemical sensor such as quartz crystal microbalance. The study of this apparatus required the preliminary synthesis of original complexing BTP-derived structures. The last part of this work deals with the study of new synthetic ways to afford the BTP moiety. The palladium-catalyzed cross-coupling reaction of 3-methylthio-1,2,4-triazine with various 2-stannylated pyridines have been explored. Our investigations have also allowed to develop a method for synthesizing unsymmetrical 1,2,4,5-tetrazine from the cross-coupling reaction between 3-methylthio-6-(morpholine-N-yl)-1,2,4,5-tetrazine and organoboron / organo-stannane derivatives. (author)

  6. Acetylene-Based Materials in Organic Photovoltaics

    Directory of Open Access Journals (Sweden)

    Fabio Silvestri

    2010-04-01

    Full Text Available Fossil fuel alternatives, such as solar energy, are moving to the forefront in a variety of research fields. Organic photovoltaic systems hold the promise of a lightweight, flexible, cost-effective solar energy conversion platform, which could benefit from simple solution-processing of the active layer. The discovery of semiconductive polyacetylene by Heeger et al. in the late 1970s was a milestone towards the use of organic materials in electronics; the development of efficient protocols for the palladium catalyzed alkynylation reactions and the new conception of steric and conformational advantages of acetylenes have been recently focused the attention on conjugated triple-bond containing systems as a promising class of semiconductors for OPVs applications. We review here the most important and representative (polyarylacetylenes that have been used in the field. A general introduction to (polyarylacetylenes, and the most common synthetic approaches directed toward making these materials will be firstly given. After a brief discussion on working principles and critical parameters of OPVs, we will focus on molecular arylacetylenes, (copolymers containing triple bonds, and metallopolyyne polymers as p-type semiconductor materials. The last section will deal with hybrids in which oligomeric/polymeric structures incorporating acetylenic linkages such as phenylene ethynylenes have been attached onto C60, and their use as the active materials in photovoltaic devices.

  7. An improved synthesis of [[sup 125]I]N-(diethylaminoethyl)-4-iodobenzamide: a potential ligand for imaging malignant melanoma

    Energy Technology Data Exchange (ETDEWEB)

    John, C.S.; Reba, R.C.; Varma, V.M.; McAfee, J.G. (Georgetown Univ. Medical Center, Washington, DC (United States)); Saga, T.; Kinuya, S.; Le, N.; Jeong, J.M.; Paik, C.H. (National Insts. of Health, Bethesda, MD (United States))

    1993-01-01

    To improve the radiolabeling yield and the specific activity of [[sup 125]I]N-(2-diethylaminoethyl)-4-iodobenzamide(DAB), the aryltributyltin precursor was synthesized from the N-(2-diethylaminoethyl)-4-bromobenzamide derivative by palladium catalyzed stannylation using bis(tributyltin). The radiolabeled product, [[sup 125]I]DAB, was obtained by an iododestannylation reaction in high radiochemical yields (85-94%, radiochemical purity, > 98%) using chloramine-T as an oxidizing agent. The specific activity was greater than 1600 Ci/mmol. The biodistribution studies in nude mice implanted with human malignant melanoma xenograft showed a good tumor uptake (6.14% ID/g at 1 h, 2.81% ID/g at 6 h and 0.42% ID/g at 24 h) of [[sup 125]I]DAB. Unfortunately, a high uptake in the non-target organs, such as liver and lung was found. At 1 h post-injection the activity level in liver and lung was 11.76 and 7.58% ID/g, respectively. A slow clearance of activity from liver and lung was observed at 6 h (3.43 and 0.49% ID/g). These results demonstrate that iodinated IDAB is a potential radiopharmaceutical for the management of patients with malignant melanoma. (Author).

  8. The Effect of Temperature on Selectivity in the Oscillatory Mode of the Phenylacetylene Oxidative Carbonylation Reaction.

    Science.gov (United States)

    Parker, Julie; Novakovic, Katarina

    2017-08-05

    Reaction temperature plays a major role in product selectivity in the oscillatory mode of the palladium-catalyzed phenylacetylene oxidative carbonylation reaction. At 40 °C, dimethyl (2Z)-2-phenyl-2-butenedioate is the major product whereas at 0 °C the major product is 5,5-dimethoxy-3-phenyl-2(5H)-furanone. The occurrence of oscillations in pH coincides with an increase in the rate of phenylacetylene consumption and associated product formation. Experiments were performed isothermally in a reaction calorimeter to correlate reactant consumption and product formation with the occurrence of pH oscillations and the heat released by the reaction. An increase in the size of the pH drop in a single oscillation correlates with an increase in energy, indicating that this section of a single oscillation relates to reactant consumption. Based on these observations, a reaction pathway responsible for product formation is provided. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

  9. Charge transport behavior of benodithiophene-diketopyrrololpyrrole-based conjugated polymer in organic field-effect transistors

    Energy Technology Data Exchange (ETDEWEB)

    Park, Jin Kuen [Dept. of Chemistry, Hankuk University of Foreign Studies, Yongin (Korea, Republic of)

    2015-07-15

    Organic optoelectronic devices, such as light-emitting diodes, organic solar cells (OSCs), and organic field effect transistors (OFETs), have emerged due to the development of π-conjugated polymers. Because the delocalized π-framework can significantly reduce the energy gap between the highest-occupied molecular orbital (HOMO) and the lowest-unoccupied molecular orbital (LUMO), their intrinsic optoelectronic properties can be tunable with their conjugation length in terms of average molecular weights and their π-backbone structures. The new type of low bandgap conjugated polymer (P1) has been successively polymerized via a palladium- catalyzed Stille cross-coupling reaction with bis-ethylhexyl BDT and bis-n-decane DPP. With a linear alkyl chain in the DPP units, the intermolecular packing structure was thought to be enhanced by proving the UV–Vis and UPS spectra. In addition, the electronic properties of P1 via field-effect transistors well illustrate the typical p-type semiconducting property without showing the significant improvement by thermal annealing. From a broader perspective, this research indicates that a wider choice of linear alkyl chain length in DPP units and modification of the interface between dielectric and active layers should be sought to further optimize device performance. Hence, progressive works with the strategy presented in this report will be pursued to address the different challenges in attaining target OFET performances.

  10. Naphthacenodithiophene Based Polymers-New Members of the Acenodithiophene Family Exhibiting High Mobility and Power Conversion Efficiency

    KAUST Repository

    Knall, Astrid Caroline; Ashraf, Raja Shahid; Nikolka, Mark; Nielsen, Christian B.; Purushothaman, Balaji; Sadhanala, Aditya; Hurhangee, Michael; Broch, Katharina; Harkin, David J.; Nová k, Jiří ; Neophytou, Marios; Hayoz, Pascal; Sirringhaus, Henning; McCulloch, Iain

    2016-01-01

    Wide-bandgap conjugated polymers with a linear naphthacenodithiophene (NDT) donor unit are herein reported along with their performance in both transistor and solar cell devices. The monomer is synthesized starting from 2,6-dihydroxynaphthalene with a double Fries rearrangement as the key step. By copolymerization with 2,1,3-benzothiadiazole (BT) via a palladium-catalyzed Suzuki coupling reaction, NDT-BT co-polymers with high molecular weights and narrow polydispersities are afforded. These novel wide-bandgap polymers are evaluated as the semiconducting polymer in both organic field effect transistor and organic photovoltaic applications. The synthesized polymers reveal an optical bandgap in the range of 1.8 eV with an electron affinity of 3.6 eV which provides sufficient energy offset for electron transfer to PC70BM acceptors. In organic field effect transistors, the synthesized polymers demonstrate high hole mobilities of around 0.4 cm2 V–1 s–1. By using a blend of NDT-BT with PC70BM as absorber layer in organic bulk heterojunction solar cells, power conversion efficiencies of 7.5% are obtained. This value is among the highest obtained for polymers with a wider bandgap (larger than 1.7 eV), making this polymer also interesting for application in tandem or multijunction solar cells. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

  11. Efficient synthesis of RITA and its analogues: derivation of analogues with improved antiproliferative activity via modulation of p53/miR-34a pathway.

    Science.gov (United States)

    Lin, Jinshun; Jin, Xiuli; Bu, Yiwen; Cao, Deliang; Zhang, Nannan; Li, Shangfu; Sun, Qinsheng; Tan, Chunyan; Gao, Chunmei; Jiang, Yuyang

    2012-12-28

    A novel approach to synthesize RITA by practical palladium-catalyzed C-C bond-forming Suzuki reactions at room temperature was developed, which was used for deriving a series of substituted tricyclic α-heteroaryl (furan/thiophene) analogues of RITA under mild conditions. These novel analogues showed notable antiproliferative activity against cancer cell lines with wild-type p53 (i.e., HCT116, A549, MCF-7 and K562), but much less activity in HCT116/p53(-/-) cells. In particular, compound 1f demonstrated promising antiproliferative activity compared to RITA, with IC(50) = 28 nM in MCF-7 vs. 54 nM for RITA, and cancer cell selectivity. Compound 1f markedly activated p53 in HCT116 cells at 100 nM, triggering apoptosis. Importantly, we found that both RITA and compound 1f induced G(0)/G(1) cell cycle arrest by up-regulating miR-34a, which in turn down-regulated the expression of cell cycle-related proteins CDK4 and E2F1. In summary, this study reports an effective synthetic approach for RITA and its analogues, and elucidates a novel antiproliferative mechanism of these compounds.

  12. Structure-Activity Relationships of Truncated C2- or C8-Substituted Adenosine Derivatives as Dual Acting A2A and A3 Adenosine Receptor Ligands

    Science.gov (United States)

    Hou, Xiyan; Majik, Mahesh S.; Kim, Kyunglim; Pyee, Yuna; Lee, Yoonji; Alexander, Varughese; Chung, Hwa-Jin; Lee, Hyuk Woo; Chandra, Girish; Lee, Jin Hee; Park, Seul-gi; Choi, Won Jun; Kim, Hea Ok; Phan, Khai; Gao, Zhan-Guo; Jacobson, Kenneth A.; Choi, Sun; Lee, Sang Kook; Jeong, Lak Shin

    2011-01-01

    Truncated N6-substituted-4′-oxo- and 4′-thioadenosine derivatives with C2 or C8 substitution were studied as dual acting A2A and A3 adenosine receptor (AR) ligands. The lithiation-mediated stannyl transfer and palladium-catalyzed cross coupling reactions were utilized for functionalization of the C2 position of 6-chloropurine nucleosides. An unsubstituted 6-amino group and a hydrophobic C2 substituent were required for high affinity at the hA2AAR, but hydrophobic C8 substitution abolished binding at the hA2AAR. However, most of synthesized compounds displayed medium to high binding affinity at the hA3AR, regardless of C2 or C8 substitution, and low efficacy in a functional cAMP assay. Several compounds tended to be full hA2AAR agonists. C2 substitution probed geometrically through hA2AAR-docking, was important for binding in order of hexynyl > hexenyl > hexanyl. Compound 4g was the most potent ligand acting dually as hA2AAR agonist and hA3AR antagonist, which might be useful for treatment of asthma or other inflammatory diseases. PMID:22142423

  13. Synthesis and characterisation of nitrogen-containing poly heterocyclic molecules for the complexation of polluting metal cations

    International Nuclear Information System (INIS)

    Leconte, N.

    2007-12-01

    The recovery of actinides(III) from the mixture actinides(III)/lanthanides(III) is a great deal of the nuclear waste management. Experiences have shown that derivatives of 2,6- bis(1,2,4-triazine-3-yl)pyridine (BTP) are able to extract selectively actinides(III) from lanthanides(III). But the properties of these molecules need to be reinforced to exhibit best extraction performances and to resist to the harsh conditions of the extracting processes. Originally functionalized ligands were synthesized and tested in a radioactive medium. In a second part, this work focuses on the control and the detection of actinides(III). This could be done thanks to the use of a chemical sensor such as quartz crystal microbalance. The study of this apparatus required the preliminary synthesis of original complexing BTP-derived structures. The last part of this work deals with the study of new synthetic ways to afford the BTP moiety. The palladium-catalyzed cross-coupling reaction of 3-methylthio-1,2,4-triazine with various 2-stannylated pyridines have been explored. Our investigations have also allowed to develop a method for synthesizing unsymmetrical 1,2,4,5-tetrazine from the cross-coupling reaction between 3-methylthio-6-(morpholine-N-yl)-1,2,4,5-tetrazine and organoboron / organo-stannane derivatives. (author)

  14. Rhodium Phosphine-π-Arene Intermediates in the Hydroamination of Alkenes

    Science.gov (United States)

    Liu, Zhijian; Yamamichi, Hideaki; Madrahimov, Sherzod T.; Hartwig, John F.

    2011-01-01

    A detailed mechanistic study of the intramolecular hydroamination of alkenes with amines catalyzed by rhodium complexes of a biaryldialkylphosphine are reported. The active catalyst is shown to contain the phosphine ligand bound in a κ1, η6 form in which the arene is π-bound to rhodium. Addition of deuterated amine to an internal olefin showed that the reaction occurs by trans addition of the N-H bond across the C=C bond, and this stereochemistry implies that the reaction occurs by nucleophilic attack of the amine on a coordinated alkene. Indeed, the cationic rhodium fragment binds the alkene over the secondary amine, and the olefin complex was shown to be the catalyst resting state. The reaction was zero-order in substrate, when the concentration of olefin was high, and a primary isotope effect was observed. The primary isotope effect, in combination with the observation of the alkene complex as the resting state, implies that nucleophilic attack of the amine on the alkene is reversible and is followed by turnover-limiting protonation. This mechanism constitutes an unusual pathway for rhodium-catalyzed additions to alkenes and is more closely related to the mechanism for palladium-catalyzed addition of amide N-H bonds to alkenes. PMID:21309512

  15. Ag1 Pd1 Nanoparticles-Reduced Graphene Oxide as a Highly Efficient and Recyclable Catalyst for Direct Aryl C-H Olefination.

    Science.gov (United States)

    Hu, Qiyan; Liu, Xiaowang; Wang, Guoliang; Wang, Feifan; Li, Qian; Zhang, Wu

    2017-12-14

    The efficient and selective palladium-catalyzed activation of C-H bonds is of great importance for the construction of diverse bioactive molecules. Despite significant progress, the inability to recycle palladium catalysts and the need for additives impedes the practical applications of these reactions. Ag 1 Pd 1 nanoparticles-reduced graphene oxide (Ag 1 Pd 1 -rGO) was used as highly efficient and recyclable catalyst for the chelation-assisted ortho C-H bond olefination of amides with acrylates in good yields with a broad substrate scope. The catalyst can be recovered and reused at least 5 times without losing activity. A synergistic effect between the Ag and Pd atoms on the catalytic activity was found, and a plausible mechanism for the AgPd-rGO catalyzed C-H olefination is proposed. These findings suggest that the search for such Pd-based bimetallic alloy nanoparticles is a new method towards the development of superior recyclable catalysts for direct aryl C-H functionalization under mild conditions. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Thermal and Dielectric Behavior Studies of Poly(Arylene Ether Sulfones with Sulfonated and Phosphonated Pendants

    Directory of Open Access Journals (Sweden)

    Shimoga D. Ganesh

    2016-01-01

    Full Text Available The present paper discusses the aspects of the synthesizing valeric acid based poly(ether sulfones with active carboxylic acid pendants (VALPSU from solution polymerization technique via nucleophilic displacement polycondensation reaction among 4,4′-dichlorodiphenyl sulfone (DCDPS and 4,4′-bis(4-hydroxyphenyl valeric acid (BHPA. The conditions necessary to synthesize and purify the polymer were investigated in some detail. The synthesized poly(ether sulfones comprise sulfone and ether linkages in addition to reactive carboxylic acid functionality; these active carboxylic acid functional groups were exploited to hold the phenyl sulphonic acid and phenyl phosphonic acid pendants. The phenyl sulphonic acid pendants in VALPSU were easily constructed by altering active carboxylic acid moieties by sulfanilic acid using N,N′-dicyclohexylcarbodiimide (DCC mediated mild synthetic route, whereas the latter one was built in two steps. Initially, polyphosphoric acid condensation with VALPSU by 4-bromoaniline and next straightforward palladium catalyzed synthetic route, in both of which acidic pendants are clenched by polymer backbone via amide linkage. Without impairing the primary polymeric backbone modified polymers were prepared by varying the stoichiometric ratios of respective combinations. All the polymers were physicochemically characterized and pressed into tablets; electrical contacts were established to study the dielectric properties. Finally, the influence of the acidic pendants on the dielectric properties was examined.

  17. Chemo-Enzymatic Synthesis of Chiral Epoxides Ethyl and Methyl (S-3-(Oxiran-2-ylpropanoates from Renewable Levoglucosenone: An Access to Enantiopure (S-Dairy Lactone

    Directory of Open Access Journals (Sweden)

    Aurélien A. M. Peru

    2016-07-01

    Full Text Available Chiral epoxides—such as ethyl and methyl (S-3-(oxiran-2-ylpropanoates ((S-1a/1b—are valuable precursors in many chemical syntheses. Until recently, these compounds were synthesized from glutamic acid in four steps (deamination, reduction, tosylation and epoxide formation in low to moderate overall yield (20%–50%. Moreover, this procedure requires some harmful reagents such as sodium nitrite ((ecotoxic and borane (carcinogen. Herein, starting from levoglucosenone (LGO, a biobased chiral compound obtained through the flash pyrolysis of acidified cellulose, we propose a safer and more sustainable chemo-enzymatic synthetic pathway involving lipase-mediated Baeyer-Villiger oxidation, palladium-catalyzed hydrogenation, tosylation and treatment with sodium ethoxide/methoxide as key steps. This route afforded ethyl and methyl (S-3-(oxiran-2-ylpropanoates in 57% overall yield, respectively. To demonstrate the potentiality of this new synthetic pathway from LGO, the synthesis of high value-added (S-dairy lactone was undertaken from these epoxides and provided the target in 37% overall yield from LGO.

  18. A stereodivergent strategy to both product enantiomers from the same enantiomer of a stereoinducing catalyst: agelastatin A.

    Science.gov (United States)

    Trost, Barry M; Dong, Guangbin

    2009-07-13

    In this article, we report a full account of our recent development of pyrroles and N-alkoxyamides as new classes of nucleophiles for palladium-catalyzed AAA reactions, along with application of these methodologies in the total synthesis of agelastatin A, a marine natural product with exceptional anticancer activity and other biological properties. Our method allows for access to either regioisomer of the pyrrolopiperazinones (6 and 19) with high efficiency and enantioselectivity. Note that isomer 19 was obtained via a cascade reaction through a double allylic alkylation pathway. From regioisomer 6, the total synthesis of (+)-agelastatin A was completed in a very short fashion (four steps from 6), during the course of which we developed a new copper catalyst for aziridination and an In(OTf)(3)/DMSO system to oxidatively open an N-tosyl aziridine. Starting with the other pyrrolopiperazinone 19, a five-step sequence has been developed to furnish a formal total synthesis of (-)-agelastatin A. A unique feature of our syntheses is the use of two rather different strategies for the total syntheses of both enantiomers of agelastatin A using the same enantiomer of a chiral palladium catalyst.

  19. Naphthacenodithiophene Based Polymers-New Members of the Acenodithiophene Family Exhibiting High Mobility and Power Conversion Efficiency

    KAUST Repository

    Knall, Astrid Caroline

    2016-08-18

    Wide-bandgap conjugated polymers with a linear naphthacenodithiophene (NDT) donor unit are herein reported along with their performance in both transistor and solar cell devices. The monomer is synthesized starting from 2,6-dihydroxynaphthalene with a double Fries rearrangement as the key step. By copolymerization with 2,1,3-benzothiadiazole (BT) via a palladium-catalyzed Suzuki coupling reaction, NDT-BT co-polymers with high molecular weights and narrow polydispersities are afforded. These novel wide-bandgap polymers are evaluated as the semiconducting polymer in both organic field effect transistor and organic photovoltaic applications. The synthesized polymers reveal an optical bandgap in the range of 1.8 eV with an electron affinity of 3.6 eV which provides sufficient energy offset for electron transfer to PC70BM acceptors. In organic field effect transistors, the synthesized polymers demonstrate high hole mobilities of around 0.4 cm2 V–1 s–1. By using a blend of NDT-BT with PC70BM as absorber layer in organic bulk heterojunction solar cells, power conversion efficiencies of 7.5% are obtained. This value is among the highest obtained for polymers with a wider bandgap (larger than 1.7 eV), making this polymer also interesting for application in tandem or multijunction solar cells. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

  20. Formation of quinones, indanones and furans by the reaction of molybdenum carbene complexes with alkynes

    International Nuclear Information System (INIS)

    Doetz, K.H.; Larbig, H.

    1992-01-01

    (Alkoxy)carbene complexes of molybdenum react with terminal alkynes to give carbene annulation of cycloaddition products, the skeleton of which depends on the carbene substitution pattern and the alkyne used. (CO) 5 Mo=C(OMe)-p-tol undergoes carbene annulation upon reaction with trimethylsilylacetylene leading to naphthoquinone after oxidative work-up. Similar products are obtained from (CO) 5 Mo=C(OMe)2-furyl and hex-1-yne or oct-1-yne. The reaction of these alkynes results in the formation of indanones as five-membered annulation products. In the presence of 3.3-dimethylbut-1-yne the (phenyl) carbene ligands act as a C 1 -synthon, which is incorporated into the furan cycloaddition products

  1. [: an expert report by Dr. Egas Moniz on homosexuality].

    Science.gov (United States)

    Molina Artaloytia, Francisco

    2016-01-01

    At the beginning of the 20th century, the noted Nobel prize-winning Portuguese neurologist Egas Moniz made an expert analysis on homosexuality in a marriage annulment case of major value as an example of the effective application of sexological knowledge of that period. Contemporary republican legislation established marriage annulment in medical terms and punished relations between persons of the same sex, or contra natura. In his report, Moniz attempted to interpret distinctive elements of the life of the subject using sexological categories, illustrating the interaction between these categories and the changing forms adopted by homosexuality (or homosexual people) of the time.

  2. Protecting-Group-Free Synthesis of 2-Deoxy-Aza-Sugars

    Directory of Open Access Journals (Sweden)

    Mattie Simon Maria Timmer

    2009-12-01

    Full Text Available The protecting-group-free asymmetric synthesis of 1,2,4-trideoxy-1,4-imino-L-xylitol is readily achieved in five steps from 2-deoxy-D-ribose and with an overall yield of 48%. Key in this synthesis is the application of our recently developed Vasella-reductive amination and carbamate annulation methodologies to the synthesis of 2-deoxy-aza-sugars. The carbamate annulation occurred with excellent yield and diastereoselectively (>20:1 d.r., in favour of the 3,4-cis isomer.

  3. Recent decision of the Constitutional Court concerning the admissibility of the referendum on nuclear power plants

    International Nuclear Information System (INIS)

    Pomodoro, Sergio.

    1981-01-01

    This paper provides a thorough analysis of the decision of the Constitutional Court on 13 February 1981 ruling that a request for a referendum whose purpose was to have adopted a partial annulment of Act no. 393 of 1975 on nuclear power plant siting was inadmissible. The decision is based on the ground that, firstly the Constitution does not allow a referendum for annulment of an Act to be held and secondly, this request ran counter to the objectives fixed by the Euratom Treaty (Community nuclear power development) to which Italy, as a Party, was committed. (NEA) [fr

  4. Strategy Toward the Total Synthesis of Epothilones A and B

    Science.gov (United States)

    1999-07-01

    would result in the formation of a secondary neopentyl center. Further evidence that the initial step in the annulation sequence is conjugate addition...0.37 mmol) was dissolved in anhydrous benzene (10 mL) and ethylene glycol (2.1 mL, 37 mmol) was added followed by p-toluenesulfonic acid (7 mg, 0.04

  5. Non bis in idem : De ontwikkeling van een beginsel

    NARCIS (Netherlands)

    van Hattum, W.F.

    2012-01-01

    Non bis in idem. The development of a principle The double jeopardy rule forbids a second prosecution for the same offence. The rule is applicable after irrevocable judgments: condemnations as well as acquittals. If a conviction is subsequently found to be wrong, it is annulled. But what if an

  6. Where Human Rights Meet Administrative Law: Essential Elements and Limits to Delegation: European Court of Justice, Grand Chamber C-355/10: European Parliament v. Council of the European Union

    NARCIS (Netherlands)

    den Heijer, M.; Tauschinsky, E.

    2013-01-01

    Case C-355/10 deals with institutional questions and with the delicate issue of intercepting migrants at sea, and thus with fundamental rights. The European Parliament had sought the annulment of a decision of the Council, adopted under the regulatory procedure with scrutiny (PRAC), on the grounds

  7. Total Synthesis of Plukenetione A

    Science.gov (United States)

    Zhang, Qiang; Mitasev, Branko; Qi, Ji; Porco, John A.

    2010-01-01

    We describe an alkylative dearomatization/acid-mediated adamantane annulation sequence which allows facile access to type A polyprenylated acylphloroglucinol (PPAP) natural products including plukenetione A. Introduction of the 2-methyl-1-propenyl moiety was achieved via stereodivergent SN2 and SN1 cyclizations of allylic alcohol substrates. PMID:20843036

  8. Act no. 933 of 11 August 1960. Establishment of the National Nuclear Energy Commission

    International Nuclear Information System (INIS)

    1960-01-01

    This Act which sets up the Comitato Nazionale per l'Energia Nucleare (CNEN) abolishes at the same time the National Committee for Nuclear Research (Comitato nazionale per le ricerche nucleari). This present Act No. 933 was subsequently annulled by Act No. 1240 of 15 December 1971 with the exception of Sections 12 to 16 which remained valid. (NEA) [fr

  9. 29 CFR 528.6 - Review.

    Science.gov (United States)

    2010-07-01

    ... 29 Labor 3 2010-07-01 2010-07-01 false Review. 528.6 Section 528.6 Labor Regulations Relating to... MINIMUM WAGE RATES § 528.6 Review. Any employer and, when appropriate, any apprenticeship agency or... order of annulment or withdrawal may obtain review, limited to the question of whether the findings of...

  10. Systemic humiliation as daily social suffering

    DEFF Research Database (Denmark)

    Rothbart, Daniel; Poder, Poul

    2017-01-01

    and capacities of these people. Drawing upon recent developments in social identity theory, moral philosophy, sociological theory, and clinical psychology, we argue that systemic humiliation generates social pain that is experienced as annulment of one’s inherent value; it is an affront to suffering persons...

  11. A systematic catalogue of the Coleopterous family Helotidae in the Leiden Museum

    NARCIS (Netherlands)

    Ritsema, C.

    1915-01-01

    Gen. HELOTA Mc L.1) Mc Leay, Annulosa Javanica, 1825, p. 42; ed. Lequien, 1833, p. 151. INDOMALAYAN SPECIES. (Nos. 1—69). 1. Vigorsi Mc L. Annul. Javan. 1825, p. 43, tab. 1, fig. 9; ed. Lequien, 1833, p. 152, tab. 5, fig. 4. a. ♀. Java or.: Mt. Ardjoeno (W. E. J. Hekmeyer). b. ♀. Java (A. B. v.

  12. Base-catalyzed bicyclization of dialkyl glutaconates with cinnamoylacetamides: a synthetic strategy for isoquinolinedione derivatives.

    Science.gov (United States)

    Li, Lei; Zhao, Yu-Long; Wang, He; Li, Yi-Jin; Xu, Xianxiu; Liu, Qun

    2014-06-21

    We report here that polysubstituted dihydroisoquinolones and isoquinolones can be constructed by the one-pot reaction of the readily available acyclic α,β-unsaturated carbonyl precursors and dialkyl glutaconates under mild basic conditions (1-45 min for the former vs. 1-6 h for the latter) via the domino process involving [3+3] annulation/intramolecular aza-cyclization.

  13. 21 CFR 1404.325 - What happens if I do business with an excluded person in a covered transaction?

    Science.gov (United States)

    2010-04-01

    ... person, we may disallow costs, annul or terminate the transaction, issue a stop work order, debar or... person in a covered transaction? 1404.325 Section 1404.325 Food and Drugs OFFICE OF NATIONAL DRUG CONTROL... Regarding Transactions Doing Business with Other Persons § 1404.325 What happens if I do business with an...

  14. 34 CFR 85.325 - What happens if I do business with an excluded person in a covered transaction?

    Science.gov (United States)

    2010-07-01

    ... person, we may disallow costs, annul or terminate the transaction, issue a stop work order, debar or... in a covered transaction? 85.325 Section 85.325 Education Office of the Secretary, Department of... Regarding Transactions Doing Business with Other Persons § 85.325 What happens if I do business with an...

  15. 22 CFR 1006.325 - What happens if I do business with an excluded person in a covered transaction?

    Science.gov (United States)

    2010-04-01

    ... disallow costs, annul or terminate the transaction, issue a stop work order, debar or suspend you, or take... person in a covered transaction? 1006.325 Section 1006.325 Foreign Relations INTER-AMERICAN FOUNDATION GOVERNMENTWIDE DEBARMENT AND SUSPENSION (NONPROCUREMENT) Responsibilities of Participants Regarding Transactions...

  16. 22 CFR 208.325 - What happens if I do business with an excluded person in a covered transaction?

    Science.gov (United States)

    2010-04-01

    ... person, we may disallow costs, annul or terminate the transaction, issue a stop work order, debar or... person in a covered transaction? 208.325 Section 208.325 Foreign Relations AGENCY FOR INTERNATIONAL... Regarding Transactions Doing Business with Other Persons § 208.325 What happens if I do business with an...

  17. 7 CFR 3017.325 - What happens if I do business with an excluded person in a covered transaction?

    Science.gov (United States)

    2010-01-01

    ... knowingly do business with an excluded person, we may disallow costs, annul or terminate the transaction... in a covered transaction? 3017.325 Section 3017.325 Agriculture Regulations of the Department of... DEBARMENT AND SUSPENSION (NONPROCUREMENT) Responsibilities of Participants Regarding Transactions § 3017.325...

  18. 22 CFR 1508.325 - What happens if I do business with an excluded person in a covered transaction?

    Science.gov (United States)

    2010-04-01

    ... person, we may disallow costs, annul or terminate the transaction, issue a stop work order, debar or... person in a covered transaction? 1508.325 Section 1508.325 Foreign Relations AFRICAN DEVELOPMENT... Regarding Transactions Doing Business with Other Persons § 1508.325 What happens if I do business with an...

  19. 22 CFR 513.225 - Failure to adhere to restrictions.

    Science.gov (United States)

    2010-04-01

    ... shall not knowingly do business under a covered transaction with a person who is— (1) Debarred or... excluded from the covered transaction. (b) Violation of the restriction under paragraph (a) of this section may result in disallowance of costs, annulment or termination of award, issuance of a stop work order...

  20. 2 CFR 180.325 - What happens if I do business with an excluded person in a covered transaction?

    Science.gov (United States)

    2010-01-01

    ... person, the Federal agency responsible for your transaction may disallow costs, annul or terminate the... excluded person in a covered transaction? 180.325 Section 180.325 Grants and Agreements OFFICE OF... Regarding Transactions Doing Business With Other Persons § 180.325 What happens if I do business with an...

  1. 29 CFR 1471.325 - What happens if I do business with an excluded person in a covered transaction?

    Science.gov (United States)

    2010-07-01

    ... business with an excluded person, we may disallow costs, annul or terminate the transaction, issue a stop... covered transaction? 1471.325 Section 1471.325 Labor Regulations Relating to Labor (Continued) FEDERAL... of Participants Regarding Transactions Doing Business with Other Persons § 1471.325 What happens if I...

  2. Nonbiomineralized carapaces in Cambrian seafloor landscapes (Sirius Passet, Greenland)

    DEFF Research Database (Denmark)

    Mangano, M. Gabriela; Bromley, Richard Granville; Harper, David A. T.

    2012-01-01

    a significant role. Although some trace fossils (e.g., annulated structures) may be related to scavenging and/or deposit feeding, morphologic evidence suggests that this is not always the case. Interconnected burrow systems provide evidence for re-use of structures, suggesting grazing on or farming of bacteria...

  3. The Challenges of Transitional Justice in Nigeria: Echoes from the ...

    African Journals Online (AJOL)

    Nonetheless, the victims' petitions were heard, to that effect, neither retributive nor restorative justice was offered to them. As tradition permits, the report will usually be published and implemented immediately. Nigerians waited patiently without recourse. Six months later, the Government of Obasanjo surprisingly annulled ...

  4. Carbohydrate carbocyclization by a zinc-mediated tandem reaction and ring-closing enyne metathesis

    DEFF Research Database (Denmark)

    Poulsen, Carina Storm; Madsen, Robert

    2002-01-01

    reaction, an amino group can be introduced in the 1,7-enyne products. Addition of 2-TMS-ethynylcerium(III) chloride after the reductive ring-opening produces the corresponding 1,6-enynes. Further annulation of the product 1,3-dienes can be achieved through a Diels-Alder reaction with good control of stereo...

  5. 48 CFR 3.402 - Statutory requirements.

    Science.gov (United States)

    2010-10-01

    ... that, for breach or violation of the warranty by the contractor, the Government may annul the contract.... Contractors' arrangements to pay contingent fees for soliciting or obtaining Government contracts have long... policy but permitted certain exceptions. These statutes— (a) Require in every negotiated contract a...

  6. 27 CFR 71.72 - Before citation.

    Science.gov (United States)

    2010-04-01

    ... 27 Alcohol, Tobacco Products and Firearms 2 2010-04-01 2010-04-01 false Before citation. 71.72... Procedure Surrender of Permit § 71.72 Before citation. If a respondent surrenders the permit before citation... appropriate TTB officer, warrants citation for suspension, revocation or annulment, the surrender shall be...

  7. The Passing-on Defence Catapulted Out of State Aid Law

    DEFF Research Database (Denmark)

    Ølykke, Grith Skovgaard

    2017-01-01

    The annotated judgment concerns the aftermath of a differentiated taxation on travelling. The General Court partially annulled the Commission’s decision and found that the recovery of the aid should be limited to the advantage actually retained by the airlines, taking into account the competitive...

  8. Perspectives on the terrestrial organic matter transport and burial along the land-deep sea continuum: Caveats in our understanding of biogeochemical processes and future needs

    Digital Repository Service at National Institute of Oceanography (India)

    Kandasamy, S.; Nath, B.N.

    ; Selvaraj et al., 2015). Interestingly, the Taiwanese rivers are characterized by hyperpycnal mode of transport and storm-hyperpycnal delivery may contribute up to 40% of annul sediment supply, but just within∼1% of time (Kao andMilliman, 2008) and therefore...

  9. Act No. 1240 of 15 December 1971. Regulations concerning the restructuring of the National Nuclear Energy Commission (CNEN)

    International Nuclear Information System (INIS)

    1972-01-01

    This Act which annuls the preceding Act of 1960 with the exception of Sections 12 to 16, confirms the CNEN's responsibilities. As opposed to the previous Act this Act contains provisions concerning the National Institute for Nuclear Physics (INFN). (NEA) [fr

  10. Neothada hades n.sp. from South Africa, with notes on the genus ...

    African Journals Online (AJOL)

    Neothada hades n.sp. from South Africa is characterized by the posession of small but distinct stylet knobs, 149-175 body annules intersected by 14 longitudinal lines (incisures), protruding lateral fields marked by four incisures, and an elongate-conoid tail with bluntly rounded tip. Reasons are given why N. canceilata ...

  11. 38 CFR 3.202 - Evidence from foreign countries.

    Science.gov (United States)

    2010-07-01

    ..., marriage, annulment, divorce, or death, provided it bears the signature and seal of the custodian of such... birth, marriage, or death, provided it bears the signature or seal or stamp of the custodian of such... general purposes and the document bears his or her signature and seal; or (3) When the document is...

  12. A Multistep Synthesis Featuring Classic Carbonyl Chemistry for the Advanced Organic Chemistry Laboratory

    Science.gov (United States)

    Duff, David B.; Abbe, Tyler G.; Goess, Brian C.

    2012-01-01

    A multistep synthesis of 5-isopropyl-1,3-cyclohexanedione is carried out from three commodity chemicals. The sequence involves an aldol condensation, Dieckmann-type annulation, ester hydrolysis, and decarboxylation. No purification is required until after the final step, at which point gravity column chromatography provides the desired product in…

  13. Nematoda: Tylenchidae

    African Journals Online (AJOL)

    1996-02-05

    Feb 5, 1996 ... 149-175 body annules intersected by 14 longitudinal lines (incisures), protruding lateral fields marked by four incisures, and an ... line, while the two outer lines are mere continuations of lon- gitudinal lines from further ..... Andrassy (1982), is possibly a printer's error, since no other. Neotliada (1o(1ulation ...

  14. Asymmetric Formation of Bridged Benzoxazocines through an Organocatalytic Multicomponent Dienamine-Mediated One-Pot Cascade

    DEFF Research Database (Denmark)

    Ransborg, Lars Krogager; Overgaard, Mette Kiilerich; Hejmanowska, Joanna

    2014-01-01

    An organocatalytic one-pot cascade leading to the stereoselective formation of novel bridged benzoxazocines is presented. The developed methodology is based on the first example of a γ-selective-Mannich-initiated cascade reaction and allows for direct annulation of the bridged benzoxazocines...

  15. A new practical approach towards the synthesis of unsymmetric and symmetric 1,10-phenanthroline derivatives at room temperature.

    Science.gov (United States)

    Cheng, Yongfeng; Han, Xuesong; Ouyang, Huangche; Rao, Yu

    2012-03-18

    An efficient method towards synthesis of 1,10-phenanthrolines is described. Through Lewis acid-catalyzed annulation reaction between 3-ethoxycyclobutanones and 8-aminoquinolines, a variety of unsymmetric and symmetric 1,10-phenanthroline derivatives were readily prepared with high regioselectivity at room temperature.

  16. 11. Jacinta M. Maweu A Critical Assessment of Odera Oruka's ...

    African Journals Online (AJOL)

    Maweu

    The issues of crime and punishment have been of great concern to human beings for a long time. This is probably because they touch on human dignity either directly or ... is itself a reward, compensation or a kind of annulment of a crime.

  17. THE LEGAL STATUS OF COMPANIES UNDER THE NEW CIVIL CODE

    Directory of Open Access Journals (Sweden)

    Lucian Bernd SĂULEANU

    2017-10-01

    Full Text Available The new Civil Code sets provisions regarding the liability of shareholders, organization and functioning of legal entity, annulment of documents issued by the management bodies of the legal entity, company contract, regime of contributions, company types, simple partnership, unlimited, simple limited partnership, with limited liability, joint stock, partnership limited by shares, cooperatives, other type of company.

  18. 8 CFR 216.4 - Joint petition to remove conditional basis of lawful permanent resident status for alien spouse.

    Science.gov (United States)

    2010-01-01

    ... of the marriage through annulment, divorce, or the death of the petitioning spouse, or if the... concurrently with the parent, the death of the parent, or other reasons may file a separate Petition to Remove... provided with written notification of the termination and the reasons therefor, and a notice to appear...

  19. 5 CFR 831.644 - Remarriage.

    Science.gov (United States)

    2010-01-01

    ... remarriage by death, annulment, or divorce if— (1) The surviving spouse elects to receive this annuity... for Government employees, by reason of the remarriage; and (2) Any lump sum paid on termination of the... the remarriage by death or divorce. (2) If present or future entitlement to a former spouse annuity is...

  20. 8 CFR 1216.4 - Joint petition to remove conditional basis of lawful permanent resident status for alien spouse.

    Science.gov (United States)

    2010-01-01

    ... the termination of the marriage through annulment, divorce, or the death of the petitioning spouse, or... concurrently with the parent, the death of the parent, or other reasons may file a separate Petition to Remove... residence. The alien shall be provided with written notification of the termination and the reasons therefor...

  1. Annual Status Report (FY2104) Composite Analysis of Low Level Waste Disposal in the Central Plateau at the Hanford Site

    Energy Technology Data Exchange (ETDEWEB)

    Nichols, W. E. [CH2M Hill Plateau Remediation Company, Richland, WA (United States)

    2015-03-24

    In accordance with U.S. Department of Energy requirements in DOE O 435.1 and as implemented by DOE/RL-2009-29, the DOE Richland Operations Office has prepared this annul summary of the Hanford Site Composite Analysis for fiscal year 2014.

  2. 29 CFR 528.2 - Definition of terms.

    Science.gov (United States)

    2010-07-01

    ... ESTABLISHMENTS AT SPECIAL MINIMUM WAGE RATES § 528.2 Definition of terms. As used in the regulations contained in... 29 Labor 3 2010-07-01 2010-07-01 false Definition of terms. 528.2 Section 528.2 Labor Regulations Relating to Labor (Continued) WAGE AND HOUR DIVISION, DEPARTMENT OF LABOR REGULATIONS ANNULMENT OR...

  3. Viral mimicry of the complement system

    Indian Academy of Sciences (India)

    The complement system is a potent innate immune mechanism consisting of cascades of proteins which are designed to fight against and annul intrusion of all the foreign pathogens. Although viruses are smaller in size and have relatively simple structure, they are not immune to complement attack. Thus, activation of the ...

  4. IMPROVING THE RULES ON PARENTAL RESPONSIBILITY FOR THE UPBRINGING OF CHILDREN IN THE CONTEXT OF MEASURES TO STRENGTHEN THE LEGAL PROTECTION OF THE FAMILY IN RUSSIA

    Directory of Open Access Journals (Sweden)

    Tatyana Krasnova

    2015-10-01

    Full Text Available This article discusses the issues of family-legal protection of children in the non-performance of parent’s responsibilities for their care and maintenance. In particular, problems associated with the separation the children from the parents, application of rules on annulment and restriction of parental rights. The author of article suggests ways to improving the Russian family legislation.

  5. Does C-reactive protein independently predict mortality in adult community-acquired bacteremia patients with known sepsis severity?

    DEFF Research Database (Denmark)

    Gradel, Kim O; Jensen, Thøger G; Kolmos, Hans J

    2013-01-01

    We evaluated whether sepsis severity and C-reactive protein (CRP) level on admission prognostically corroborated or annulled each other in adult patients with incident community-acquired bacteremia (Funen, Denmark, 2000-2008). We used logistic regression and area under the receiver operating.......06), thus CRP contributed as much as sepsis severity to prognosis....

  6. Salt stress induced changes in germination, lipid peroxidation and ...

    African Journals Online (AJOL)

    Final germination percentage (FG%) decreased with increasing salinity in GL, Paris Island cos and Isadora varieties, and was annulated at the highest salt concentration in GL, the most sensitive variety. However, in the less sensitive, KS, FG% was decreased by 60% compared to the control at 200 mM. KS and GL varieties ...

  7. Synthesis of rearranged unsaturated drimane derivatives

    Directory of Open Access Journals (Sweden)

    Miranda Domingos S. de

    2001-01-01

    Full Text Available A full account to the preparation and application of three appropriately substituted vinylcyclohexenes (2,2-dimethyl-3-vinylcyclohex-3-en-1-ol, 2,2-dimethyl-3-vinylcyclohex-3-en-1-one and 3,3-dimethyl-2-vinylcyclohexene in thermal Diels-Alder reactions with alpha,beta-unsaturated esters (methyl tiglate and methyl angelate is given. This approach delivered the racemic synthesis of ten octalin derivatives bearing a rearranged drimane skeleton (4 diastereomers of 1-methoxycarbonyl-6-hydroxy-1,2,5,5-tetramethyl-1,2,3,5,6,7, 8,8a-octahydronaphthalene; 1-methoxycarbonyl-6-oxo-1,2,5,5-tetramethyl-1,2,3,4,5,6,7,8-octahydronaphthalene; 2-methoxycarbonyl-6-oxo-1,2,5,5-tetramethyl-1,2,3,5,6,7,8,8a-octahydronaphthalene; 3 diastereomers of 1-methoxycarbonyl-1,2,5,5-tetramethyl-1,2,3,5,6,7,8,8a-octahydronaphthalene and 2-methoxycarbonyl-1,2,5,5-tetramethyl-1,2,3,5,6,7,8,8a-octahydronaphthalene . Central synthetic features included preparation of enoltriflates by Stang's protocol and the successful palladium-catalyzed cross-coupling reaction (Stille reaction of the triflate with the tri-n-butylvinylstannane. The octalins relative stereochemistry was unequivocally ascertained by spectroscopic methods and/or X-ray crystallography and these data now stand as useful tools to support the correct assignment of related natural products usually isolated in minute amounts.

  8. New ferrocenic pyrrolo[1,2-a]quinoxaline derivatives: synthesis, and in vitro antimalarial activity.

    Science.gov (United States)

    Guillon, Jean; Moreau, Stéphane; Mouray, Elisabeth; Sinou, Véronique; Forfar, Isabelle; Fabre, Solene Belisle; Desplat, Vanessa; Millet, Pascal; Parzy, Daniel; Jarry, Christian; Grellier, Philippe

    2008-10-15

    Following our search for antimalarial compounds, novel series of ferrocenic pyrrolo[1,2-a]quinoxaline derivatives 1-2 were synthesized from various substituted nitroanilines and tested for in vitro activity upon the erythrocytic development of Plasmodiumfalciparum strains with different chloroquine-resistance status. The pyrrolo[1,2-a]quinoxalines 1 were prepared in 6-8 steps through a regioselective palladium-catalyzed monoamination by coupling 4-chloropyrrolo[1,2-a]quinoxalines with 1,3-bis(aminopropyl)piperazine or -methylamine using Xantphos as the ligand. The ferrocenic bispyrrolo[1,2-a]quinoxalines 2 were prepared by reductive amination of previously described bispyrrolo[1,2-a]quinoxalines 9 with ferrocene-carboxaldehyde, by treatment with NaHB(OAc)(3). The best results were observed with ferrocenic pyrrolo[1,2-a]quinoxalines linked by a bis(3-aminopropyl)piperazine. Moreover, it was observed that a methoxy group on the pyrrolo[1,2-a]quinoxaline nucleus and no substitution on the terminal N-ferrocenylmethylamine function enhanced the pharmacological activity. Selected compounds 1b, 1f-h, 1l and 2a were tested for their ability to inhibit beta-haematin formation, the synthetic equivalent of hemozoin, by using the HPIA (heme polymerization inhibitory activity) assay. Of the tested compounds, only 2a showed a beta-haematin formation inhibition, but no inhibition of haem polymerization was observed with the other selected ferrocenic monopyrrolo[1,2-a]quinoxaline derivatives 1b, 1f-h and 1l, as the IC(50) values were superior to 10 equivalents.

  9. Radiosynthesis and autoradiographic evaluation of [{sup 11}C]NAD-299, a radioligand for visualization of the 5-HT{sub 1A} receptor

    Energy Technology Data Exchange (ETDEWEB)

    Sandell, Johan E-mail: Johan.Sandell@psyk.ks.se; Halldin, Christer; Hall, Haakan; Thorberg, Seth-Olov; Werner, Tom; Sohn, Daniel; Sedvall, Goeran; Farde, Lars

    1999-02-01

    The selective 5-HT{sub 1A} receptor antagonist NAD-299 ([R]-3-N,N-dicyclobutylamino-8-fluoro-3,4-dihydro-2H-1-benzopyran- 5-carboxamide) was labeled with the positron emitting radionucldie carbon-11. The radioligand was synthesized from NAD-195 ([R]-3-N,N-dicyclobutylamino-8-fluoro-5-trifluoromethylsulfonyloxy-3, 4-dihydro-2H-1-benzopyran) in two radiochemical steps. A palladium-catalyzed reaction of NAD-195 and [{sup 11}C]cyanide was followed by hydrolysis of the carbon-11-labeled nitrile intermediate with basic hydrogen peroxide. The total radiochemical yield, based on [{sup 11}C]CO{sub 2} and corrected for decay, was 20-40%. The specific radioactivity was 24 GBq/{mu}mol (900 Ci/mmol) at end of synthesis, with a radiochemical purity better than 99% and a total synthesis time of 40-45 min. Autoradiographic examination of [{sup 11}C]NAD-299 binding in human brain postmortem demonstrated high binding in hippocampus, raphe nuclei, and neocortex. The binding in the hippocampus was higher than in the neocortex. Within the hippocampus, the densest binding was observed in the CA1 region. [{sup 11}C]NAD-299 binding was inhibited by addition of the 5-HT{sub 1A} receptor ligands WAY-100635, pindolol, ({+-})-8-OH-DPAT, 5-HT, and buspirone, leaving a low background of nonspecific binding. The results indicate that [{sup 11}C]NAD-299 binds specifically to 5-HT{sub 1A} receptors in the human brain in vitro and is a potential radioligand for positron emission tomography (PET) examination of 5-HT{sub 1A} receptors in vivo.

  10. Bis(carbazol-9-ylphenyl)aniline end-capped oligoarylenes as solution-processed nondoped emitters for full-emission color tuning organic light-emitting diodes.

    Science.gov (United States)

    Khanasa, Tanika; Prachumrak, Narid; Rattanawan, Rattanawaree; Jungsuttiwong, Siriporn; Keawin, Tinnagon; Sudyoadsuk, Taweesak; Tuntulani, Thawatchai; Promarak, Vinich

    2013-07-05

    A series of bis(3,6-di-tert-butylcarbazol-9-ylphenyl)aniline end-capped oligoarylenes, BCPA-Ars, are synthesized by double palladium-catalyzed cross-coupling reactions. By using this bis(carbazol-9-yl)triphenylamine moiety as an end-cap, we are able to reduce the crystallization and retain the high-emission ability of these planar fluorescent oligoarylene cores in the solid state, as well as improve the amorphous stability and solubility of the materials. The results of optical and electrochemical studies show that their HOMOs, LUMOs, and energy gaps can be easily modified or fine-tuned by either varying the degree of π-conjugation or using electron affinities of the aryl cores which include fluorene, oligothiophenes, 2,1,3-benzothiadiazole, 4,7-diphenyl-4-yl-2,1,3-benzothiadiazole, and 4,7-dithien-2-yl-2,1,3-benzothiadiazole. As a result, their emission spectra measured in solution and thin films can cover the full UV-vis spectrum (426-644 nm). Remarkably, solution-processed nondoped BCPA-Ars-based OLEDs could show moderate to excellent device performance with emission colors spanning the whole visible spectrum (deep blue to red). Particularly, the RGB (red, green, blue) OLEDs exhibit good color purity close to the pure RGB colors. This report offers a practical approach for both decorating the highly efficient but planar fluorophores and tuning their emission colors to be suitable for applications in nondoped and solution-processable full-color emission OLEDs.

  11. Radiosynthesis and autoradiographic evaluation of [11C]NAD-299, a radioligand for visualization of the 5-HT1A receptor

    International Nuclear Information System (INIS)

    Sandell, Johan; Halldin, Christer; Hall, Haakan; Thorberg, Seth-Olov; Werner, Tom; Sohn, Daniel; Sedvall, Goeran; Farde, Lars

    1999-01-01

    The selective 5-HT 1A receptor antagonist NAD-299 ([R]-3-N,N-dicyclobutylamino-8-fluoro-3,4-dihydro-2H-1-benzopyran- 5-carboxamide) was labeled with the positron emitting radionucldie carbon-11. The radioligand was synthesized from NAD-195 ([R]-3-N,N-dicyclobutylamino-8-fluoro-5-trifluoromethylsulfonyloxy-3, 4-dihydro-2H-1-benzopyran) in two radiochemical steps. A palladium-catalyzed reaction of NAD-195 and [ 11 C]cyanide was followed by hydrolysis of the carbon-11-labeled nitrile intermediate with basic hydrogen peroxide. The total radiochemical yield, based on [ 11 C]CO 2 and corrected for decay, was 20-40%. The specific radioactivity was 24 GBq/μmol (900 Ci/mmol) at end of synthesis, with a radiochemical purity better than 99% and a total synthesis time of 40-45 min. Autoradiographic examination of [ 11 C]NAD-299 binding in human brain postmortem demonstrated high binding in hippocampus, raphe nuclei, and neocortex. The binding in the hippocampus was higher than in the neocortex. Within the hippocampus, the densest binding was observed in the CA1 region. [ 11 C]NAD-299 binding was inhibited by addition of the 5-HT 1A receptor ligands WAY-100635, pindolol, (±)-8-OH-DPAT, 5-HT, and buspirone, leaving a low background of nonspecific binding. The results indicate that [ 11 C]NAD-299 binds specifically to 5-HT 1A receptors in the human brain in vitro and is a potential radioligand for positron emission tomography (PET) examination of 5-HT 1A receptors in vivo

  12. False Testimony and Oath: Reopening a Legal Case in Iranian Courts

    Directory of Open Access Journals (Sweden)

    Iman Zeajeldi

    2017-02-01

    Full Text Available In Iranian legal laws, hearing a case ends by issuing the final judgment. However, the law has provided conditions where the individuals can apply for retrial so that their rights will be protected and losses will be prevented. This means that court will rehear a case for which it has issued a final judgment. Now, each of the parties to the claim who has applied for reopening must prove the conditions of reopening. One of the conditions is proving the falsehood in the claim. Yet, the question is ‘under which conditions the falsehood brings about the annulment of the judgment issued’. The present research aims to study the effects of falsehood cases in the possibility of applying for reopening and annulling the judgment issued.

  13. Heat transfer and flow characteristics around a finned-tube bank heat exchanger in fluidized bed

    International Nuclear Information System (INIS)

    Honda, Ryosuke; Umekawa, Hisashi; Ozawa, Mamoru

    2009-01-01

    Principal heat transfer mechanisms in a fluidized bed have been classified into three categories, i.e. solid convection, gas convection and radiation. Among these mechanisms, the solid convection is a dominant mechanism in the bubbling fluidized bed. This solid convection is substantially caused by the bubble movement, thus the visualization of the void fraction distribution becomes a very useful method to understand the characteristics of the fluidized-bed heat exchanger. In this study, the heat transfer coefficient and the void fraction around the heat transfer tube with annuler fin were measured. For the quantitative measurement of the void fraction, neutron radiography and image processing technique were employed. Owing to the existence of the annuler fin, the restriction of the particle movements was put. This restriction suppressed the disturbance caused by tubes, and the influence of the tube arrangement on the flow and heat transfer characteristics could be clearly expressed.

  14. Heat transfer and flow characteristics around a finned-tube bank heat exchanger in fluidized bed

    Energy Technology Data Exchange (ETDEWEB)

    Honda, Ryosuke [Department of Mechanical Engineering, Kansai University, 3-3-35 Yamate-cho, Suita, Osaka 564-8680 (Japan); Umekawa, Hisashi [Department of Mechanical Engineering, Kansai University, 3-3-35 Yamate-cho, Suita, Osaka 564-8680 (Japan)], E-mail: umekawa@kansai-uac.jp; Ozawa, Mamoru [Department of Mechanical Engineering, Kansai University, 3-3-35 Yamate-cho, Suita, Osaka 564-8680 (Japan)

    2009-06-21

    Principal heat transfer mechanisms in a fluidized bed have been classified into three categories, i.e. solid convection, gas convection and radiation. Among these mechanisms, the solid convection is a dominant mechanism in the bubbling fluidized bed. This solid convection is substantially caused by the bubble movement, thus the visualization of the void fraction distribution becomes a very useful method to understand the characteristics of the fluidized-bed heat exchanger. In this study, the heat transfer coefficient and the void fraction around the heat transfer tube with annuler fin were measured. For the quantitative measurement of the void fraction, neutron radiography and image processing technique were employed. Owing to the existence of the annuler fin, the restriction of the particle movements was put. This restriction suppressed the disturbance caused by tubes, and the influence of the tube arrangement on the flow and heat transfer characteristics could be clearly expressed.

  15. Highly Stereoselective Synthesis of Cyclopentanes bearing Four Stereocenters by a Rhodium Carbene–Initiated Domino Sequence

    Science.gov (United States)

    Parr, Brendan T.; Davies, Huw M. L.

    2014-01-01

    Stereoselective synthesis of a cyclopentane nucleus by convergent annulations constitutes a significant challenge for synthetic chemists. Though a number of biologically relevant cyclopentane natural products are known, more often than not, the cyclopentane core is assembled in a stepwise fashion due to lack of efficient annulation strategies. Herein, we report the rhodium-catalyzed reactions of vinyldiazoacetates with (E)-1,3-disubstituted 2-butenols generate cyclopentanes, containing four new stereogenic centers with very high levels of stereoselectivity (99% ee, >97 : 3 dr). The reaction proceeds by a carbene–initiated domino sequence consisting of five distinct steps: rhodium–bound oxonium ylide formation, [2,3]-sigmatropic rearrangement, oxy-Cope rearrangement, enol–keto tautomerization, and finally an intramolecular carbonyl ene reaction. A systematic study is presented detailing how to control chirality transfer in each of the four stereo-defining steps of the cascade, consummating in the development of a highly stereoselective process. PMID:25082301

  16. Rh(III)-Catalyzed Synthesis of N-Unprotected Indoles from Imidamides and Diazo Ketoesters via C-H Activation and C-C/C-N Bond Cleavage.

    Science.gov (United States)

    Qi, Zisong; Yu, Songjie; Li, Xingwei

    2016-02-19

    The synthesis of N-unprotected indoles has been realized via Rh(III)-catalyzed C-H activation/annulation of imidamides with α-diazo β-ketoesters. The reaction occurs with the release of an amide coproduct, which originates from both the imidamide and the diazo as a result of C═N cleavage of the imidamide and C-C(acyl) cleavage of the diazo. A rhodacyclic intermediate has been isolated and a plausible mechanism has been proposed.

  17. Analysis of Body Mass Index and First-Term Attrition of Navy Enlisted Personnel

    Science.gov (United States)

    2017-06-01

    personnel, it exacerbates demands on recruiters who already face difficult recruiting goals… The GAO estimated that in fiscal year 1996 alone , the...people to change eating habits that results in weight change. 17 As previously stated, the study sample in Kivimaki et al. looks at men and women...interlocutory), and “single” for those who do not have a spouse they are providing for (single, annulled, divorced, legally separated, never married

  18. Perylene-fused BODIPY dye with near-IR absorption/emission and high photostability

    KAUST Repository

    Jiao, Chongjun

    2011-02-18

    A N-annulated perylene unit was successfully fused to the meso-and β-positions of a boron dipyrromethene (BODIPY) core. The newly synthesized BODIPY dye 1b exhibits intensified near-infrared (NIR) absorption and the longest emission maximum ever observed for all BODIPY derivatives. In addition, this dye possesses excellent solubility and photostability, beneficial to practical applications. © 2011 American Chemical Society.

  19. Dementia and Legal Competency

    OpenAIRE

    Filaković, Pavo; Petek Erić, Anamarija; Mihanović, Mate; Glavina, Trpimir; Molnar, Sven

    2011-01-01

    The legal competency or capability to exercise rights is level of judgment and decision-making ability needed to manage one's own affairs and to sign official documents. With some exceptions, the person entitles this right in age of majority. It is acquired without legal procedures, however the annulment of legal capacity requires a juristic process. This resolution may not be final and could be revoked thorough the procedure of reverting legal capacity – fully or partially. Given ...

  20. Les chercheurs inquiets malgre les promesses de Claudie Haignere

    CERN Multimedia

    2003-01-01

    "Le 9 avril, lors d'un colloque sur l'innovation, la ministre deleguee a la recherche et aux nouvelles technologies a annonce, "en plein accord, dit-elle, avec le premier ministre", que "les etablissements publics a caractere scientifique et technologique (EPST) ne connaitront en 2003 aucune nouvelle annulation de credits de paiement et d'autorisations de programme" et que "les reserves de precaution sont entierement levees" (1 page).

  1. Journal of Chemical Sciences | Indian Academy of Sciences

    Indian Academy of Sciences (India)

    A novel and facile one-pot synthesis of 1-substituted tetrahydro--carbolines by cyclocondensation of ketene ,–acetals with tryptamine in presence of InCl3 and TFA as co-catalysts by Bischler-Napieralski cyclization is described. The reaction involves formation of one C-N bond, one C-C bond and a new ring annulation ...

  2. Fractures obstétricales lors des césariennes au CHU de Yopougon ...

    African Journals Online (AJOL)

    Les lésions associées étaient représentées par six paralysies du plexus brachial (POPB) type Duchenne Erb. Le traitement était orthopédique dans tous les cas avec un bon pronostic. Notre étude montre que la césarienne n'annule pas le risque de fracture obstétricale. Une meilleure maîtrise de la dynamique obstétricale ...

  3. Superior Administrative Court Baden-Wuerttemberg. Judgement of March 30, 1982 (Wyhl)

    International Nuclear Information System (INIS)

    Anon.

    1983-01-01

    Presentation and discussion of the leading statements of the decision delivered by the Mannheim Superior Administrative Court on March 30, 1982 concerning the Wyhl nuclear power plant, unit 1. With this decision, covering 548 pages, the Superior Administrative Court changed the decision of the Freiburg Administrative Court of the year 1977 and finally dismissed the action for annulment of the construction licence. The Superior Administrative Court acted upon the appeal brought in by the Land and the plant operator, Kernkraftwerksgesellschaft. (CB) [de

  4. Convergent Synthesis of Piperidines by the Union of Conjugated Alkynes with Imines: A Unique Regioselective Bond Construction for Heterocycle Synthesis

    Science.gov (United States)

    Chen, Ming Z.; Micalizio, Glenn C.

    2009-01-01

    A two-step process is described for the union of aromatic imines, conjugated alkynes and aldehydes that results in a stereoselective synthesis of highly substituted piperidines. This synthetic process has been made possible by defining a unique regioselective functionalization of conjugated alkynes that establishes a suitably functionalized substrate for subsequent heterocycle-forming cationic annulation. Given the flexibility of the coupling process, heterocycles can be accessed through a process that establishes up to four stereogenic centers and four fused rings. PMID:19817447

  5. Dynamic Response of Vertebral Elements Related to USAF Injury

    Science.gov (United States)

    1978-02-01

    eventual loss of mucopolysaccharide matrix from both the hyaline cartilage end plates and fibro- cartilage annulUS« resulting in increased cell...In other studies conducted during this contract period, seven adult Rhesus monkeys have been subjected to implantations of calibrated stress...fibroblasts; 2. Loss of cells from and compression of the circular regions lying between the cartilage end plates and nucleus; 3. Altered staining and

  6. Le nouveau modèle africain | IDRC - International Development ...

    International Development Research Centre (IDRC) Digital Library (Canada)

    22 juil. 2011 ... L'annulation de la dette, un commerce plus équitable, davantage d'aide : voilà le plan d'action mondial dont on convient qu'il faut de toute urgence mettre en oeuvre en vue d'accélérer le développement en Afrique. Or, ce serait rater le bateau que de ne pas s'engager dans la voie tout autre que les ...

  7. 2,2,7-Trichloro-3,4-dihydronaphthalen-1(2H-one

    Directory of Open Access Journals (Sweden)

    Ben Capuano

    2009-09-01

    Full Text Available The title compound, C10H7Cl3O, obtained as a major byproduct from a classical Schmidt reaction. The cyclohexyl ring is distorted from a classical chair conformation, as observed for monocyclic analogues, presumably due to conjugation of the planar annulated benzo ring and the ketone group (r.m.s. deviation 0.024 Å. There are no significant intermolecular interactions.

  8. Perylene-fused BODIPY dye with near-IR absorption/emission and high photostability

    KAUST Repository

    Jiao, Chongjun; Huang, Kuo-Wei; Wu, Jishan

    2011-01-01

    A N-annulated perylene unit was successfully fused to the meso-and β-positions of a boron dipyrromethene (BODIPY) core. The newly synthesized BODIPY dye 1b exhibits intensified near-infrared (NIR) absorption and the longest emission maximum ever observed for all BODIPY derivatives. In addition, this dye possesses excellent solubility and photostability, beneficial to practical applications. © 2011 American Chemical Society.

  9. Development of the Vinylogous Pictet-Spengler Cyclization and Total Synthesis of (±)-Lundurine A.

    Science.gov (United States)

    Nash, Aaron; Qi, Xiangbing; Maity, Pradip; Owens, Kyle; Tambar, Uttam K

    2018-04-16

    A novel vinylogous Pictet-Spengler cyclization has been developed for the generation of indole-annulated medium-sized rings. The method enables the synthesis of tetrahydroazocinoindoles with a fully substituted carbon center, a prevalent structural motif in many biologically active alkaloids. The strategy has been applied to the total synthesis of (±)-lundurine A. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. THE RULE OF NON-IMMEDIATE ESTOPPEL OF ART. 1.009, § 1º AND THE COMBINATION WITH THE ART. 278: PROTEST ANTI LIMIT ON CPC/2015?

    Directory of Open Access Journals (Sweden)

    Vinicius Silva Lemos

    2018-04-01

    Full Text Available The present study analyzes the change in the system of estoppel of interlocutory decisions taken by novel order procedure, with the view of conflict of norm among the art. 1,009, paragraph 1 and article 278 which provides for the nullity of procedure - absolute and relative - and the consequent estoppel. Before the conflict, we analyze the possible solutions before this conflict of norms and the attempt of systematization of estoppel - of the annulments and interlocutory.

  11. Iodine-Mediated Intramolecular Dehydrogenative Coupling: Synthesis of N-Alkylindolo[3,2-c]- and -[2,3-c]quinoline Iodides.

    Science.gov (United States)

    Volvoikar, Prajesh S; Tilve, Santosh G

    2016-03-04

    An I2/TBHP-mediated intramolecular dehydrogenative coupling reaction is developed for the synthesis of a library of medicinally important 5,11-dialkylindolo[3,2-c]quinoline salts and 5,7-dimethylindolo[2,3-c]quinoline salts. The annulation reaction is followed by aromatization to yield tetracycles in good yield. This protocol is also demonstrated for the synthesis of the naturally occurring isocryptolepine in salt form.

  12. Gender, mental illness and the Hindu Marriage Act, 1955.

    Science.gov (United States)

    Pathare, Soumitra; Nardodkar, Renuka; Shields, Laura; Bunders, Joske F G; Sagade, Jaya

    2015-01-01

    Section 5(ii) of The Hindu Marriage Act, 1955 (HMA) states that under certain circumstances, mental illness is accepted as a ground for the annulment of marriage, while Section 13(1) (iii) states that mental illness is a ground for divorce. There is little data on how this provision is used and applied in matrimonial petitions. This paper assesses judicial practices in divorce cases, exploring the extent to which gender and the diagnosis of mental illness affect the decision to grant annulment or divorce. The paper analyses judgments related to annulment and divorce at the Family Court in Pune and at the High Courts in India. In the Family Court at Pune, 85% of the cases were filed by husbands, who alleged that their spouse was mentally ill. Medical evidence of mental illness was presented in only 36% of the cases and in many cases, divorce/nullity was granted even in the absence of medical evidence. In 14% of the cases, nullity/divorce was granted even when both spouses were not present. Of the Family Court cases reaching the High Court, 95% were filed by male petitioners. The High Courts reversed the lower courts' judgments in 50% of the cases. Our analysis highlights the need for standardised guidelines for lower courts on what constitutes adequate medical proof of mental illness when hearing a petition related to nullity or divorce under HMA. It also provides a critical review of Section 5(ii) of HMA.

  13. Fused thiophene-based conjugated polymers and their use in optoelectronic devices

    Science.gov (United States)

    Facchetti, Antonio; Marks, Tobin J.; Takai, Atsuro; Seger, Mark; Chen; , Zhihua

    2017-07-18

    The present teachings relate to polymeric compounds and their use as organic semiconductors in organic and hybrid optical, optoelectronic, and/or electronic devices such as photovoltaic cells, light emitting diodes, light emitting transistors, and field effect transistors. The disclosed compounds generally include as repeating units at least one annulated thienyl-vinylene-thienyl (TVT) unit and at least one other pi-conjugated unit. The annulated TVT unit can be represented by the formula: ##STR00001## where Cy.sup.1 and Cy.sup.2 can be a five- or six-membered carbocyclic ring. The annulated TVT unit can be optionally substituted at any available ring atom(s), and can be covalently linked to the other pi-conjugated unit via either the thiophene rings or the carbocyclic rings Cy.sup.1 and Cy.sup.2. The other pi-conjugated unit can be a conjugated linear linker including one or more unsaturated bonds, or a conjugated cyclic linker including one or more carbocyclic and/or heterocyclic rings.

  14. Extreme electronic modulation of the cofacial porphyrin structural motif.

    Science.gov (United States)

    Fletcher, James T; Therien, Michael J

    2002-04-24

    The synthesis, electrochemistry, and optical spectroscopy of an extensive series of cofacial bis[(porphinato)zinc(II)] compounds are reported. These species were synthesized using sequential palladium-catalyzed cross-coupling and cobalt-mediated [2+2+2] cycloaddition reactions. This modular methodology enables facile control of the nature of macrocycle-to-macrocycle connectivity and allows unprecedented modulation of the redox properties of face-to-face porphyrin species. We report the synthesis of 5,6-bis[(5',5''-10',20'-bis[4-(3-methoxy-3-methylbutoxy)phenyl]porphinato)zinc(II)]indane (1), 5,6-bis[(2'-5',10',15',20'-tetraphenylporphinato)zinc(II)]indane (2), 5-([2'-5',10',15',20'-tetraphenylporphinato]zinc(II))-6-[(5"-10'',20''-bis[4-(3-methoxy-3-methylbutoxy)phenyl]porphinato)zinc(II)]indane (3), 5-([2'-5',10',15',20'-tetrakis(trifluoromethyl)porphinato]zinc(II))-6-[(5' '-10' ',20' '-bis[4-(3-methoxy-3-methylbutoxy)phenyl]porphinato)zinc(II)]indane (4), 5-(2'-5',10',15',20'-[tetrakis(trifluoromethyl)porphinato]zinc(II))-6-[(2''-5'',10'',15'',20''-tetraphenylporphinato)zinc(II)]indane (5), 5,6-bis([2'-5',15'-diphenyl-10',20'-(trifluoromethyl)porphinato]zinc(II))indane (6), and 5,6-bis([2'-5',10',15',20'-tetrakis(trifluoromethyl)porphinato]zinc(II))indane (7); 4-7 define the first examples of cofacial bis[(porphinato)metal] compounds in which sigma-electron-withdrawing perfluoroalkyl groups serve as macrocycle substituents, while 2, 6, and 7 constitute the first such structures that possess a beta-to-beta linkage topology. Cyclic voltammetric studies show that the electrochemically determined HOMO and LUMO energy levels of these cofacial bis(porphinato) complexes can be lowered by 780 and 945 mV, respectively, relative to the archetypal members of this class of compounds; importantly, these orbital energy levels can be modulated over well-defined increments throughout these wide potentiometric domains. Analyses of these cofacial bis

  15. Synthesis, in vitro validation and in vivo pharmacokinetics of [{sup 125}I]N-[2-(4-iodophenyl)ethyl]-N-methyl-2-(1-piperidinyl) ethylamine: A high-affinity ligand for imaging sigma receptor positive tumors

    Energy Technology Data Exchange (ETDEWEB)

    John, Christy S; Gulden, Mary E; Vilner, Bertold J; Bowen, Wayne D

    1996-08-01

    N-[2-(4-iodophenyl)ethyl]-N-methyl-2-(1-piperidinyl)ethylamine, IPEMP, and the corresponding bromo derivative, BrPEMP, have been synthesized and characterized. Both BrPEMP and IPEMP were evaluated for sigma-1 and sigma-2 subtype receptor affinities and found to possess very high affinities for both receptor subtypes. The precursor for radioiodination n-tributylstannylphenylethylpiperidinylethylamine was prepared from its bromo derivative by palladium-catalyzed stannylation reaction. Radioiodinated 4-[{sup 125}I]PEMP was readily prepared in high yields and high specific activity by oxidative iododestannylation reaction using chloramine-T as oxidizing agent. Sites labeled by 4-[{sup 125}I]PEMP in guinea pig brain membranes showed high affinity for BD1008, haloperidol, and (+)-pentazocine (Ki = 5.06 {+-} 0.40, 32.6 {+-} 2.75, and 48.1 {+-} 8.60 nM, respectively), which is consistent with sigma receptor pharmacology. Competition binding studies of 4-[{sup 125}I]PEMP in melanoma (A375) and MCF-7 breast cancer cells showed a high affinity, dose-dependent inhibition of binding with known sigma ligand N-[2-(3,4-dichlorophenyl)ethyl]-N-methyl-2-(1-pyrrolidinyl) ethylamine, BD1008 (Ki = 5, 11 nM, respectively), supporting the labeling of sigma sites in these cells. Haloperidol, however showed a weaker (Ki 100-200 nM) affinity for the sites labeled by 4-[{sup 125}I]PEMP in these cells. Biodistribution studies of 4-[{sup 125}I]PEMP in rats showed a fast clearance of this radiopharmaceutical from blood, liver, lung, and other organs. A co-injection of 4-IPEMP with 4-[{sup 125}I]PEMP resulted in 37%, 69%, and 35% decrease in activity in liver, kidney, and brain (organs possessing sigma receptors), respectively at 1-h postinjection. These results suggest that 4-[{sup 125}I]PEMP is a promising radiopharmaceutical for pursuing further studies in animal models with tumors.

  16. Synthesis and PET studies of [(11)C-cyano]letrozole (Femara), an aromatase inhibitor drug.

    Science.gov (United States)

    Kil, Kun-Eek; Biegon, Anat; Ding, Yu-Shin; Fischer, Andre; Ferrieri, Richard A; Kim, Sung Won; Pareto, Deborah; Schueller, Michael J; Fowler, Joanna S

    2009-02-01

    Aromatase, a member of the cytochrome P450 family, converts androgens such as androstenedione and testosterone into estrone and estradiol, respectively. Letrozole (1-[bis-(4-cyanophenyl)methyl]-1H-1,2,4-triazole; Femara) is a high-affinity aromatase inhibitor (K(i)=11.5 nM) that has Food and Drug Administration approval for breast cancer treatment. Here we report the synthesis of carbon-11-labeled letrozole and its assessment as a radiotracer for brain aromatase in the baboon. Letrozole and its precursor (4-[(4-bromophenyl)-1H-1,2,4-triazol-1-ylmethyl]benzonitrile) were prepared in a two-step synthesis from 4-cyanobenzyl bromide and 4-bromobenzyl bromide, respectively. The [(11)C]cyano group was introduced via tetrakis(triphenylphosphine)palladium(0)-catalyzed coupling of [(11)C]cyanide with the bromo precursor. Positron emission tomography (PET) studies in the baboon brain were carried out to assess regional distribution and kinetics, reproducibility of repeated measures and saturability. Log D, the free fraction of letrozole in plasma and the [(11)C-cyano]letrozole fraction in arterial plasma were also measured. [(11)C-cyano]Letrozole was synthesized in 60 min with a radiochemical yield of 79-80%, with a radiochemical purity greater than 98% and a specific activity of 4.16+/-2.21 Ci/mumol at the end of bombardment (n=4). PET studies in the baboon revealed initial rapid and high uptake and initial rapid clearance, followed by slow clearance of carbon-11 from the brain, with no difference between brain regions. Brain kinetics was not affected by coinjection of unlabeled letrozole (0.1 mg/kg). The free fraction of letrozole in plasma was 48.9%, and log D was 1.84. [(11)C-cyano]Letrozole is readily synthesized via a palladium-catalyzed coupling reaction with [(11)C]cyanide. Although it is unsuitable as a PET radiotracer for brain aromatase, as revealed by the absence of regional specificity and saturability in brain regions such as amygdala, which are known to

  17. Synthesis and PET studies of [11C-cyano]letrozole (Femara®), an aromatase inhibitor drug

    Science.gov (United States)

    Kil, Kun-Eek; Biegon, Anat; Ding, Yu-Shin; Fischer, Andre; Ferrieri, Richard A.; Kim, Sung Won; Pareto, Deborah; Schueller, Michael J.; Fowler, Joanna S.

    2011-01-01

    Introduction Aromatase, a member of the cytochrome P450 family, converts androgens such as androstenedione and testosterone to estrone and estradiol respectively. Letrozole (1-[bis-(4-cyanophenyl)methyl]-1H-1,2,4-triazole, Femara®) is a high affinity aromatase inhibitor (Ki=11.5 nM) which has FDA approval for breast cancer treatment. Here we report the synthesis of carbon-11 labeled letrozole and its assessment as a radiotracer for brain aromatase in the baboon. Methods Letrozole and its precursor (4-[(4-bromophenyl)-1H-1,2,4-triazol-1-ylmethyl]benzonitrile, 3) were prepared in two-step syntheses from 4-cyanobenzyl bromide and 4-bromobenzyl bromide, respectively. The [11C]cyano group was introduced via the tetrakis(triphenylphosphine)palladium(0) catalyzed coupling of [11C]cyanide with the bromo-precursor (3). PET studies in the baboon brain were carried out to assess regional distribution and kinetics, reproducibility of repeated measures and saturability. The free fraction of letrozole in the plasma, log D, and the [11C-cyano]letrozole fraction in the arterial plasma were also measured. Results [11C-cyano]Letrozole was synthesized in 60 min with a radiochemical yield of 79–80%, with a radiochemical purity greater than 98% and a specific activity of 4.16±2.21 Ci/μmol at the end of bombardment (n=4). PET studies in the baboon revealed initial rapid and high uptake and initial rapid clearance followed by slow clearance of carbon-11 from the brain with no difference between brain regions. The brain kinetics was not affected by co-injection of unlabeled letrozole (0.1 mg/kg). The free fraction of letrozole in plasma was 48.9% and log D was 1.84. Conclusion [11C-cyano]Letrozole is readily synthesized via a palladium catalyzed coupling reaction with [11C]cyanide. Although it is unsuitable as a PET radiotracer for brain aromatase as revealed by the absence of regional specificity and saturability in brain regions, such as amygdala, which are known to contain

  18. Fluorene-based narrow-band-gap copolymers for red light- emitting diodes and bulk heterojunction photovoltaic cells

    Institute of Scientific and Technical Information of China (English)

    Mingliang SUN; Li WANG; Yangjun XIA; Bin DU; Ransheng LIU; Yong CAO

    2008-01-01

    A series of narrow band-gap conjugated copo-lymers (PFO-DDQ) derived from 9,9-dioctylfluorene (DOF) and 2,3-dimethyl-5,8-dithien-2-yl-quinoxalines (DDQ) is prepaid by the palladium-catalyzed Suzuki coupling reaction with the molar feed ratio of DDQ at around 1%,5%,15%,30% and 50%,respectively.The obtained polymers are readily soluble in common organic solvents.The solutions and the thin solid films of the copolymers absorb light from 300-590 nm with two absorbance.peaks at around 380 and 490 nm.The intens-ity of 490 nm peak increases with the increasing DDQ content in the polymers.Efficient energy transfer due to exciton trapping on narrow-band-gap DDQ sites has been observed.The PL emission consists exclusively of DDQ unit emission at around 591 643 nm depending on the DDQ content in solid film.The EL emission peaks are red-shifted from 580 nm for PFO-DDQ1 to 635 nm for PFO-DDQ50.The highest external quantum efficiency achieved with the device configuration ITO/PEDOT/ PVK/PFO-DDQt5/Ba/A1 is 1.33% with a luminous effi-ciency 1.54 cd/A.Bulk heterojunction photovoltaic cells fabricated from composite films of PFO-DDQ30 copoly-mer and [6,6]-phenyl C61 butyric acid methyl ester (PCBM) as electron donor and electron acceptor,respect-ively in device configuration:ITO/PEDOT:PSS/PFO-DDQ30:PCBM/PFPNBr/Al shows power conversion effi-ciencies of 1.18% with open-circuit voltage (Voc) of 0.90 V and short-circuit current density (Jsc) of 2.66 mA/cm2 under an AM1.5 solar simulator (100 mW/cm2).The photocurrent response wavelengths of the PVCs based on PFO-DDQ30/PCBM blends covers 300-700 nm.This indicates that these kinds of low band-gap polymers are promising candidates for polymeric solar cells and red light-emitting diodes.

  19. Synthesis and PET studies of [{sup 11}C-cyano]letrozole (Femara), an aromatase inhibitor drug

    Energy Technology Data Exchange (ETDEWEB)

    Kil, Kun-Eek [Medical Department, Brookhaven National Laboratory, Upton, NY 11973 (United States); Department of Chemistry, Stony Brook University, Stony Brook, NY 11794 (United States); Biegon, Anat [Medical Department, Brookhaven National Laboratory, Upton, NY 11973 (United States); Ding, Yu-Shin [Department of Radiology, Yale University School of Medicine, New Haven, CT 06520-8048 (United States); Fischer, Andre [Johannes-Gutenberg Universitaet Mainz, Institut fuer Organische Chemie, 55128 Mainz (Germany); Ferrieri, Richard A.; Kim, Sung Won; Pareto, Deborah; Schueller, Michael J. [Medical Department, Brookhaven National Laboratory, Upton, NY 11973 (United States); Fowler, Joanna S. [Medical Department, Brookhaven National Laboratory, Upton, NY 11973 (United States); Department of Chemistry, Stony Brook University, Stony Brook, NY 11794 (United States)], E-mail: fowler@bnl.gov

    2009-02-15

    Introduction: Aromatase, a member of the cytochrome P450 family, converts androgens such as androstenedione and testosterone into estrone and estradiol, respectively. Letrozole (1-[bis-(4-cyanophenyl)methyl]-1H-1,2,4-triazole; Femara) is a high-affinity aromatase inhibitor (K{sub i}=11.5 nM) that has Food and Drug Administration approval for breast cancer treatment. Here we report the synthesis of carbon-11-labeled letrozole and its assessment as a radiotracer for brain aromatase in the baboon. Methods: Letrozole and its precursor (4-[(4-bromophenyl)-1H-1,2,4-triazol-1-ylmethyl]benzonitrile) were prepared in a two-step synthesis from 4-cyanobenzyl bromide and 4-bromobenzyl bromide, respectively. The [{sup 11}C]cyano group was introduced via tetrakis(triphenylphosphine)palladium(0)-catalyzed coupling of [{sup 11}C]cyanide with the bromo precursor. Positron emission tomography (PET) studies in the baboon brain were carried out to assess regional distribution and kinetics, reproducibility of repeated measures and saturability. Log D, the free fraction of letrozole in plasma and the [{sup 11}C-cyano]letrozole fraction in arterial plasma were also measured. Results: [{sup 11}C-cyano]Letrozole was synthesized in 60 min with a radiochemical yield of 79-80%, with a radiochemical purity greater than 98% and a specific activity of 4.16{+-}2.21 Ci/{mu}mol at the end of bombardment (n=4). PET studies in the baboon revealed initial rapid and high uptake and initial rapid clearance, followed by slow clearance of carbon-11 from the brain, with no difference between brain regions. Brain kinetics was not affected by coinjection of unlabeled letrozole (0.1 mg/kg). The free fraction of letrozole in plasma was 48.9%, and log D was 1.84. Conclusion: [{sup 11}C-cyano]Letrozole is readily synthesized via a palladium-catalyzed coupling reaction with [{sup 11}C]cyanide. Although it is unsuitable as a PET radiotracer for brain aromatase, as revealed by the absence of regional specificity

  20. One new genus and three new species of deep-sea nematodes (Nematoda: Microlaimidae) from the Southwest Pacific Ocean and Ross Sea.

    Science.gov (United States)

    Leduc, Daniel

    2016-02-11

    New deep-sea nematodes of the family Microlaimidae are described from the Southwest Pacific Ocean and Ross Sea. Microlaimus korari n. sp. is characterised by annulated cuticle with longitudinal bars, round amphideal aperture slightly smaller than the cryptospiral amphideal fovea, spacious and heavily cuticularised buccal cavity with large dorsal tooth and right subventral tooth situated anteriorly relative to left subventral tooth, slender spicules 4.4 cloacal body diameters long, and gubernaculum 1.2 cloacal body diameters long with laterally curved distal end and swollen proximal end. Bolbolaimus tongaensis n. sp. is characterised by annulated cuticle with longitudinal bars, oval amphideal aperture and cryptocircular amphideal fovea situated between cephalic setae and only partially surrounded by cuticle annulations, and short spicules cuticularised along dorsal edge and at proximal end and with swollen portion near proximal end. Maragnopsia n. gen. is characterised by a minute, non-cuticularised mouth cavity without teeth, an elongated posterior pharyngeal bulb more than twice as long as it is wide, a single outstretched testis, and a conico-cylindrical tail 13-16 anal body diameters long. A list of all 83 valid Microlaimus species is provided. The present study provides the first microlaimid species records from deep-sea habitats (> 200 m depth) in the Southwest Pacific and Ross Sea. The presence of M. korari n. sp. on both the continental slope of New Zealand and Ross Sea abyssal plain suggests that this species has a wide geographical and depth distribution. However, molecular analyses will be required to confirm the identity of these two geographically disparate populations.

  1. HARNESSING THE CHEMISTRY OF CO2

    Energy Technology Data Exchange (ETDEWEB)

    Louie, Janis

    2010-05-11

    Our research program is broadly focused on activating CO{sub 2} through the use of organic and organometallic based catalysts. Some of our methods have centered on annulation reactions of unsaturated hydrocarbons (and carbonyl substrates) to provide a diverse array of carbocycles and heterocycles. We use a combination of catalyst discovery and optimization in conjunction with classical physical organic chemistry to elucidate the key mechanistic features of the cycloaddition reactions such that the next big advances in catalyst development can be made. Key to all of our cycloaddition reactions is the use of a sterically hindered, electron donating N heterocyclic carbene (NHC) ligand, namely IPr (or SIPr), in conjunction with a low valent nickel pre-catalyst. The efficacy of this ligand is two-fold: (1) the high {delta}-donating ability of the NHC increases the nucleophilicity of the metal center which thereby facilitates interaction with the electrophilic carbonyl and (2) the steric hindrance prevents an otherwise competitive side reaction involving only the alkyne substrate. Such a system has allowed for the facile cycloaddition to prepare highly functionalized pyrones, pyridones, pyrans, as well as novel carbocycles. Importantly, all reactions proceed under extremely mild conditions (room temperature, atmospheric pressures, and short reaction times), require only catalytic amounts of Ni/NHC and readily available starting materials, and afford annulated products in excellent yields. Our current focus revolves around understanding the fundamental processes that govern these cycloadditions such that the next big advance in the cyclization chemistry of CO{sub 2} can be made. Concurrent to our annulation chemistry is our investigation of the potential for imidazolylidenes to function as thermally-actuated CO{sub 2} sequestering and delivery agents.

  2. A new species of Thelastomathidae (Nematoda) a parasite of Neocurtilla claraziana Saussure (Orthoptera, Gryllotalpidae) in Argentina.

    Science.gov (United States)

    Camino, Nora B; Maiztegui, Bárbara

    2002-07-01

    Gryllophila cephalobulata n. sp. (Nematoda, Thelastomatidae) a parasite of the mole cricket Neocurtilla claraziana (Orthoptera, Gryllotalpidae) isolated in Buenos Aires Province, is described and illustrated. It is characterized by cuticle annulated all along the length of the body; the first ring has 4 lobules, the second one has 14 lobules, the others rings are simple, the stoma is short and has 4 small teeth, the genital papillae are arranged in 5 pairs, of which 3 pairs are preanal and 2 pairs are postanal. The tail appendage of the male is long and filiform.

  3. International nuclear reactor hazard study. Design and operational features, and hazards of commercial nuclear power reactors in the world. Vol. 1

    International Nuclear Information System (INIS)

    Anderson, R.; Benecke, J.; Donderer, R.; Etemad, S.; Hirsch, H.; Kjellstroem, B.; Large, J.; Scheer, J.; Schneider, M.; Schumacher, H.; Schumacher, O.; Scott, M.; Takagi, J.; Thompson, G.; Torrie, R.; Ziggel, H.

    1986-09-01

    Project management and scientific coordination was performed by Gruppe Oekologie Hannover. The experts from Canada, the Federal Republic of Germany, France, Great Britain, Sweden, USA, and Japan represented an annulated experience of work on nuclear safety. The panel members analyzed the reactor types of their respective countries. The draft reports on the individual reactor types were discussed. Also included are brief descriptions of the different reactor types with simple drawing, evolution of reactor types and a brief report on nuclear power plants in the world. (DG)

  4. Total Synthesis of Hyperforin.

    Science.gov (United States)

    Ting, Chi P; Maimone, Thomas J

    2015-08-26

    A 10-step total synthesis of the polycyclic polyprenylated acylphloroglucinol (PPAP) natural product hyperforin from 2-methylcyclopent-2-en-1-one is reported. This route was enabled by a diketene annulation reaction and an oxidative ring expansion strategy designed to complement the presumed biosynthesis of this complex meroterpene. The described work enables the preparation of a highly substituted bicyclo[3.3.1]nonane-1,3,5-trione motif in only six steps and thus serves as a platform for the construction of easily synthesized, highly diverse PPAPs modifiable at every position.

  5. Final Environmental Assessment: C-17 Program Changes Altus Air Force Base, Oklahoma

    Science.gov (United States)

    2004-07-01

    during the summer and are part of a network of caves by bats during migration from Mexico to Kansas (USAF 1996). Five small mammal species are known to...main distribution network is presently a mix of transite, cast iron, and plastic pipes. The oldest pipes were installed during World War II, when the...8217·erages or annu!!l oporauons: ~ nerone . numbers do not round. As with the increased utilization of Lubbock lAP for C- 17 train ing purposes so also, does

  6. Problematika Putusan Hakim dalam Perkara Pembatalan Perjanjian

    Directory of Open Access Journals (Sweden)

    Nindyo Pramono

    2012-02-01

    Full Text Available The rapid development of international business law requires judges to re-scrutinise principles of contract law in the Civil Code. Therefore, principles of good faith, protection of third-party, retroaction, and restoration to pre-contract position will be analysed to provide objectively constructive feedback for judges when hearing over request for contract annulment.  Pesatnya perkembangan hukum bisnis internasional mengharuskan hakim untuk mempelajari kembali asas-asas hukum perjanjian dalam KUHPerdata. Prinsipprinsip itikad baik, perlindungan bagi pihak ketiga, retroaktif, dan kembali ke keadaan semula akan dianalisis dalam tulisan ini sehingga memberikan konstruksi obyektif kepada hakim dalam memutus permohonan pembatalan perjanjian agar jangan sampai menimbulkan perkara baru.

  7. Need for ex officio control of unfair terms in consumer contracts: comparative view of the Spanish system

    Directory of Open Access Journals (Sweden)

    Ana Isabel Blanco García

    2016-12-01

    Full Text Available European authorities advocate for providing judges greater power to examine ex officio the abusive nature of the standard contract terms within a consumer contract.  This line of reasoning in case-law has been introduced in Spain, thus improving the protection of consumers’ rights and interests. However, countries like Uruguay do not consider this possibility, preventing judges from controlling contents unless it is requested by the parties, since the annulment of a contract would be questioned due to the legal nature of nullity. In this paper, the different regulations of unfair contract terms in the Spanish and Uruguayan systems are discussed.

  8. Intramolecular Redox-Mannich Reactions: Facile Access to the Tetrahydroprotoberberine Core.

    Science.gov (United States)

    Ma, Longle; Seidel, Daniel

    2015-09-07

    Cyclic amines such as pyrrolidine undergo redox-annulations with 2-formylaryl malonates. Concurrent oxidative amine α-CH bond functionalization and reductive N-alkylation render this transformation redox-neutral. This redox-Mannich process provides regioisomers of classic Reinhoudt reaction products as an entry to the tetrahydroprotoberberine core, enabling the synthesis of (±)-thalictricavine and its epimer. An unusually mild amine-promoted dealkoxycarbonylation was discovered in the course of these studies. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Enantioselective N-Heterocyclic Carbene Catalysis via the Dienyl Acyl Azolium.

    Science.gov (United States)

    Gillard, Rachel M; Fernando, Jared E M; Lupton, David W

    2018-04-16

    Herein we report the enantioselective N-heterocyclic carbene catalyzed (4+2) annulation of the dienyl acyl azolium with enolates. The reaction exploits readily accessible acyl fluorides and TMS enol ethers to give a range of highly enantio- and diastereo-enriched cyclohexenes (most >97:3 er and >20:1 dr). The reaction was found to require high nucleophilicity NHC catalysts with mechanistic studies supporting a stepwise 1,6-addition/β-lactonization. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. The earliest cornulitid on the internal surface of the illaenid pygidium from the Middle Ordovician of Estonia

    Directory of Open Access Journals (Sweden)

    Olev Vinn

    2017-10-01

    Full Text Available The earliest cornulitid Cornulites sp. appears in the Darriwilian (Lasnamägi Regional Stage of Estonia. Internal annulation is present in all Middle Ordovician cornulitids and could be a plesiomorphic character for the group. The encrusted trilobites are rare in the Ordovician of Estonia. Illaenid pygidia and cranidia were encrusted by cornulitids and trepostome bryozoans. The encrustation of both Middle Ordovician and Late Ordovician trilobites took place post mortem. The studied hard substrate communities of Middle Ordovician and Late Ordovician trilobite pygidia and cranidia are typical of the Ordovician.

  11. Vonis Mati Bandar Dan Pengedar Narkoba Antara Putusan Mk Dan Sema (Perspektif Hukum Pidana Islam)

    OpenAIRE

    Irfan, M Nurul

    2014-01-01

    : The Dead Penalty for the Drug Dealers in the Constitutional Court and the Sema (an Islamic Criminal Law Perspective). The death sentence set by the Supreme Court for the agents and drug dealers has attracted attention of criminal law experts. Constitutional Court Decision No. 34 / PUU-X /2013 which annuls Article 268 paragraph (3) Criminal Procedure Code-stating that the submission PK (judicial review) can only be done once- has open a chance that the PK can be submitted more than once. Thi...

  12. 4-Hydroxy-3-[(2E-3-(3,4,5-trimethoxyphenylprop-2-enoyl]-2H-chromen-2-one

    Directory of Open Access Journals (Sweden)

    Lassaad Mechi

    2009-07-01

    Full Text Available A new chalcone of the coumarin, C21H18O7, containing an annulated α-pyrone ring, was obtained by condensation of the borate complex of acyl(hydroxycoumarin with trimethoxybenzaldehyde. The structure exhibits intramolecular hydrogen bonding between the hydroxyl oxygen and the ketonic oxygen in the coumarin group. The bicyclic coumarin fragment and the benzene ring form a dihedral angle of 17.1 (4°. The crystal packing involves dimers interconnected by C—H...O hydrogen bonding.

  13. Civil Law Legal Assistance; Lawyer’s Study Guide

    Science.gov (United States)

    1998-05-01

    from bigamy and incest . D. The void/voidable distinction. The grounds relating to annulment apply to voidable marriages — marriages with such defects...differences, uses neutral language [" son lives with father every other weekend"] rather than "loaded words" with win-lose implications [i.e., "custody...mutual consent" What if mom disagrees to Wednesday night supper with dad? What if dad disagrees with mom having the children on the 4th of July? What

  14. [Chloroquine analogues from benzofuro- and benzothieno[3,2-b]-4-pyridone-2-carboxylic acid esters].

    Science.gov (United States)

    Gölitzer, K; Meyer, H; Jomaa, H; Wiesner, J

    2004-08-01

    The amides 7 were synthesized from the annulated methyl 4-pyridone-2-carboxylates 4 via the carboxylic acids 5 and their acid chlorides by reacting with the novaldiamine base 6. The alcohol 8b, obtained from DIBAH reduction of the ester 4b, was transformed to the chloromethyl derivative 9 which reacted with 6 and 18-crown-6 leading to the 2-novaldiaminomethyl-4-pyridone 10. Compound 10 was obtained with higher yield from DIBAH reduction of the amide 7b. The substances 7 and 10 were inactive when tested against the chloroquine resistant Plasmodium falciparum strain Dd2.

  15. Investigation of prototypal MOFs consisting of polyhedral cages with accessible Lewis-acid sites for quinoline synthesis.

    Science.gov (United States)

    Gao, Wen-Yang; Leng, Kunyue; Cash, Lindsay; Chrzanowski, Matthew; Stackhouse, Chavis A; Sun, Yinyong; Ma, Shengqian

    2015-03-21

    A series of prototypal metal-organic frameworks (MOFs) consisting of polyhedral cages with accessible Lewis-acid sites, have been systematically investigated for Friedländer annulation reaction, a straightforward approach to synthesizing quinoline and its derivatives. Amongst them MMCF-2 demonstrates significantly enhanced catalytic activity compared with the benchmark MOFs, HKUST-1 and MOF-505, as a result of a high-density of accessible Cu(II) Lewis acid sites and large window size in the cuboctahedral cage-based nanoreactor of MMCF-2.

  16. A Small Step Towards Stricter Practice in Cases of Breach of the Treaty under Article 108(2) TFEU?

    DEFF Research Database (Denmark)

    Bach, Kasper Ullerup

    2012-01-01

    The article examines the extent to which the Court’s judgment in Case C-331/09 is in line with this case-law, especially the requirements for implementing decisions on repayment. The article starts with a review of the Commission Decision, followed by a description of the implementing measures...... taken by Poland. Next, the judgment of the Court of Justice is analysed in the light of the recent case-law. Finally, some comments are given on the course of events relating to Case C-331/09, and the partial annulment of the Decision by the General Court in Case T-1/08....

  17. Some optical properties of one dimensional annular photonic crystal with plasma frequency

    Science.gov (United States)

    Pandeya, G. N.; Thapa, Khem B.

    2018-05-01

    This paper presents the reflection bands, photonic band gaps, of the one-dimensional annul photonic crystal (APC) containing double negative (DNG) metamaterials and air. The proposed annular structure consists of the alternate layers of dispersive DNG material and air immersed in free space. The reflectance properties of the APC by employing the transfer matrix method (TMM) in the cylindrical waves for TE polarization is studied theoretically. In addition of this, we have also studied the effect of plasma frequency on the reflection behavior of the considered annular structure.

  18. [Bioethical reflections on ill-considered care due to an early diagnosis of Alzheimer disease].

    Science.gov (United States)

    Buxó, M Jesús; Casado, María

    2014-01-01

    Early diagnosis of Alzheimer disease raises important bioethical issues. In the interval between early disease detection and symptom onset, there is a time in which the patient's autonomy, privacy, and dignity may be undermined by certain healthcare measures or by family care and support. These measures may eventually turn patients into an object of care, preventing them from accepting the disease, developing an identity, and rearranging their living spaces. Every effort should be made to ensure that care does not become compassionate harassment or an invasive act, annulling the patient's autonomy, identity, and self-determination. Copyright © 2013 SESPAS. Published by Elsevier Espana. All rights reserved.

  19. LEGAL CONSEQUENCES OF MERGERS AND ACQUISITIONS

    Directory of Open Access Journals (Sweden)

    Amelia-Raluca ONIŞOR

    2016-05-01

    Full Text Available The research analyses the legal effects of mergers and acquisitions from the Romanian Company Law perspective, underlining certain general principles, the procedure of annulment of such a legal transformation of companies and the protection of the employees of companies participating in the merger according to the Law no. 67/2006. These consequences of mergers and acquisions are to be seen in the broader light of the most important purpose of this legal instrument, maximizing financial and organizational efficiencies, thus legal certainty is a desirable goal to be assumed by any merger regulation.

  20. CO2 emissions versus the carbon footprint: what are the implications for energy policies?

    International Nuclear Information System (INIS)

    Havel, Aurelien; Barbier, Laura

    2015-01-01

    With the delocalisation of industry, emissions of greenhouse gases and notably of CO 2 have been transferred from the rich world to today's manufacturing economies. This internationalisation annuls the effects of restrictive environmental legislation that has been enacted in the developed countries. If a firm has to pollute, it will relocate its production to parts of the world where environmental constraints are less restrictive, even non-existent. Yet, as regulations aimed at limiting emissions are becoming ever more widespread, the question of their redistribution between producer and consumer is now a hot subject for debate. It will be high on the agenda of COP21. (authors)

  1. Synthesis and structural and photoswitchable properties of novel chiral host molecules: axis chiral 2,2'-dihydroxy-1,1'-binaphthyl-appended stiff-stilbene.

    Science.gov (United States)

    Shimasaki, Toshiaki; Kato, Shin-ichiro; Ideta, Keiko; Goto, Kenta; Shinmyozu, Teruo

    2007-02-16

    Novel photoswitchable chiral hosts having an axis chiral 2,2'-dihydroxy-1,1'-binaphthyl (BINOL)-appended stiff-stilbene, trans-(R,R)- and -(S,S)-1, were synthesized by palladium-catalyzed Suzuki-Miyaura coupling and low-valence titanium-catalyzed McMurry coupling as key steps, and they were fully characterized by various NMR spectral techniques. The enantiomers of trans-1 showed almost complete mirror images in the CD spectra, where two split Cotton effects (exciton coupling) were observed in the beta-transitions of the naphthyl chromophore at 222 and 235 nm, but no Cotton effect was observed in the stiff-stilbene chromophore at 365 nm. The structures of (R)-10 and trans-(R,R)-1 were confirmed by X-ray structural analysis. The optimized structure of cis-1 by MO calculations has a wide chiral cavity of 7-8 A in diameter, whereas trans-1 cannot form an intramolecular cavity based on the X-ray data. Irradiation of (R,R)-trans-1 with black light (lambda = 365 nm) in CH3CN or benzene at 23 degrees C led to the conversion to the corresponding cis-isomer, as was monitored by 1H NMR, UV-vis, and CD spectra. At the photostationary state, the cis-1/trans-1 ratio was 86/14 in benzene or 75/25 in CH3CN. On the other hand, irradiation of the cis-1/trans-1 (75/25) mixture in CH3CN with an ultra-high-pressure Hg lamp at 23 degrees C (lambda = 410 nm) led to the photostationary state, where the cis-1/trans-1 ratio was estimated to be 9/91 on the basis of the 1H NMR spectra. The cis-trans and trans-cis interconversions could be repeated 10 times without decomposition of the C=C double bond. Thus, a new type of photoswitchable molecule has been developed, and trans-1 and cis-1 were quite durable under irradiation conditions. The guest binding properties of the BINOL moieties of trans- and cis-(R,R)-1 with F-, Cl-, and H2PO4- were examined by 1H NMR titration in CDCl3. Similar interaction with F- and Cl- was observed in trans-1 (host/guest = 1/1, Kassoc = (1.0 +/- 0.13) x 103 for F

  2. Synthetic strategies for controlling inter- and intramolecular interactions: Applications in single-molecule fluorescence imaging, bioluminescence imaging, and palladium catalysis

    Science.gov (United States)

    Conley, Nicholas R.

    proximity of the Cy3 and Cy5 fluorophores, behaves as an optical photoswitch in the presence of a thiol reagent. This unique property was employed to achieve sub-diffraction-limited imaging of the stalks of Caulobacter crescentus cells with 30-nm resolution using STORM (stochastic optical reconstruction microscopy). Lastly, the synthesis of the first selenium analogue of firefly luciferin is described, and this analogue is shown to be a competent substrate for firefly luciferase (fLuc). Remarkably, it exhibits red-shifted bioluminescence emission relative to the native sulfur analogue. The in vivo performance of the selenium and sulfur analogues in imaging are compared by tail-vein injection into nude mice bearing subcutaneous tumor xenografts of a human breast cancer cell line that was stably transduced to express fLuc. Part II of this thesis begins by addressing design considerations in the development of palladium catalysts that effect oxidative transformations under mild conditions (i.e., 1 atm air, room temperature) using molecular oxygen as the terminal oxidant. A newly synthesized cationic palladium complex, [(2,9-dimethylphenanthroline)Pd(OAc)]2[OTf]2, is shown to catalyze aerobic alcohol oxidation under such conditions with an unprecedented initial turnover frequency, but the presence of partially reduced oxygen species results in competitive ligand oxidation with concomitant decrease in catalyst activity. To remedy this, oxidatively resistant ligands, which are essential for the development of next-generation, high-turnover-frequency palladium catalysts that utilize oxygen as a terminal oxidant, have been prepared and effectively employed. In addition, the first general palladium-catalyzed route to the carbonylation of diols is reported. In this system, carbon monoxide (1 atm) serves the carbonyl source, (2,9-dimethylphenanthroline)Pd(OAc) 2 acts as the catalyst, and N-chlorosuccinimide and iodosobenzene are the oxidants for 1,2- and 1,3-diols, respectively. This

  3. Elucidation of Mechanisms and Selectivities of Metal-Catalyzed Reactions using Quantum Chemical Methodology.

    Science.gov (United States)

    Santoro, Stefano; Kalek, Marcin; Huang, Genping; Himo, Fahmi

    2016-05-17

    Quantum chemical techniques today are indispensable for the detailed mechanistic understanding of catalytic reactions. The development of modern density functional theory approaches combined with the enormous growth in computer power have made it possible to treat quite large systems at a reasonable level of accuracy. Accordingly, quantum chemistry has been applied extensively to a wide variety of catalytic systems. A huge number of problems have been solved successfully, and vast amounts of chemical insights have been gained. In this Account, we summarize some of our recent work in this field. A number of examples concerned with transition metal-catalyzed reactions are selected, with emphasis on reactions with various kinds of selectivities. The discussed cases are (1) copper-catalyzed C-H bond amidation of indoles, (2) iridium-catalyzed C(sp(3))-H borylation of chlorosilanes, (3) vanadium-catalyzed Meyer-Schuster rearrangement and its combination with aldol- and Mannich-type additions, (4) palladium-catalyzed propargylic substitution with phosphorus nucleophiles, (5) rhodium-catalyzed 1:2 coupling of aldehydes and allenes, and finally (6) copper-catalyzed coupling of nitrones and alkynes to produce β-lactams (Kinugasa reaction). First, the methodology adopted in these studies is presented briefly. The electronic structure method in the great majority of these kinds of mechanistic investigations has for the last two decades been based on density functional theory. In the cases discussed here, mainly the B3LYP functional has been employed in conjunction with Grimme's empirical dispersion correction, which has been shown to improve the calculated energies significantly. The effect of the surrounding solvent is described by implicit solvation techniques, and the thermochemical corrections are included using the rigid-rotor harmonic oscillator approximation. The reviewed examples are chosen to illustrate the usefulness and versatility of the adopted methodology in

  4. The Conseil d'Etat ruling to the dispute about the report from the 9. Chamber of Dispute Section - No. 370321. Regulated tariffs for the supply of natural gas - The Conseil d'Etat judges that the continuation of regulated tariffs for the supply of natural gas is contrary to E.U. law

    International Nuclear Information System (INIS)

    Lignereux, Bastien; Nicolazo de Barmon, Marie-Astrid

    2017-07-01

    The National Association of energy retailer operators (ANODE) brought proceedings to the Conseil d'Etat arguing that the decree of 16 May 2013 regarding regulated tariffs for the supply of natural gas was 'ultra vires'. The ANODE submitted that this tariff regulation breached European Union Law. Applying the findings of the preliminary ruling of 7 September 2016 given in this matter by the European Court of Justice, the Conseil d'Etat, in today's decision, annulled the decree of 16 May 2013 on the grounds that the imposition of a natural gas tariff regulation infringed European Union Law. In light of the great uncertainty that would affect contracts signed by millions of consumers as a result of such an annulment, and with regard to the necessity to prevent the legal insecurity that would ensue, the Conseil d'Etat has judged, exceptionally, that the past effects of this decree, which ceased to apply on 1 January 2016, must nevertheless be regarded as irrevocable

  5. It’s not the Fish that Stinks! EU Trade Relations with Morocco under the Scrutiny of the General Court of the European Union

    Directory of Open Access Journals (Sweden)

    Sandra Hummelbrunner

    2016-09-01

    Full Text Available The EU’s international agreements with Morocco on trade in agricultural and fishery products have drawn criticism due to their application to the disputed territory of Western Sahara, a territory that remains on the list of non-self-governing territories to be decolonised in accordance with the right of self-determination of the indigenous Sahrawi people. Recently, the Sahrawi liberation movement Front Polisario brought an action for annulment before the General Court of the European Union (GC against the Council Decision approving the conclusion of one such agreement, alleging multiple violations of European and international legal norms. Interestingly, although the GC concurred by annulling the Decision insofar as it applies to Western Sahara, it chose to exclusively base its judgment on EU fundamental rights, invoking the EU’s failure to ensure that the fundamental rights of the Sahrawi people were not infringed by applying the agreements to Western Sahara. By summarily setting aside Front Polisario’s other claims, several relevant questions of applicable international and European law, which warrant further discussion, remain. This article examines these questions using the GC’s judgment in Front Polisario, thereby combining general matters of international and European law with the specific circumstances of the EU-Morocco relations and Western Sahara.

  6. Ultrastructure of spermatogenesis in the sea star, Asterina minor.

    Science.gov (United States)

    Yamagata, A

    1988-02-01

    The ultrastructural features of spermatogenesis were investigated in the hermaphroditic sea star Asterina minor. The primordial germ cells in the genital rachis contain small clusters of electron-dense material (nuage material) and a stack of annulate lamellae. They also have a flagellum and basal body complex situated close to the Golgi complex. After the development of the genital rachis into the ovotestis, spermatogenic cells increase in number and differentiation begins. Nuage material is observed in spermatogonia, but it gradually disappears in spermatocytes. The annulate lamellae do not exist beyond the early spermatogonial stage. By contrast, a flagellum and basal body complex are found throughout spermatogenesis. The Golgi-derived proacrosomal vesicles appear in the spermatocyte and coalesce to form an acrosomal vesicle in the early spermatid. The process of acrosome formation is as follows: (1) a lamella of endoplasmic reticulum (ER) continuous with the outer nuclear membrane encloses the posterior portion of the acrosomal vesicle; (2) the vesicle attaches to the cell membrane with its anterior portion; (3) periacrosomal material accumulates in the space between the acrosomal vesicle and the ER; (4) the nucleus proper changes its features to surround the acrosome; (5) amorphous, electron-dense material is deposited under the electron-dense disk; and (6) the nucleus forms a hollow opposite the electron-dense material.

  7. Low-frequency stimulation cancels the high-frequency-induced long-lasting effects in the rat medial vestibular nuclei.

    Science.gov (United States)

    Grassi, S; Pettorossi, V E; Zampolini, M

    1996-05-15

    In rat brainstem slices, we investigated the effects of low-frequency stimulation (LFS) of the primary vestibular afferents on the amplitude of the field potentials evoked in the medial vestibular nuclei (MVN). LFS induced long-term effects, the sign of which depended on whether the vestibular neurons were previously conditioned by HFS. In unconditioned slices, LFS evoked modifications of the responses that were similar to those observed after HFS but had a smaller extension. In fact, LFS caused long-lasting potentiation of the N1 wave in the MVN ventral portion (Vp) and long-lasting depression of the N2 wave in the MVN dorsal portion (Dp), whereas it provoked small and variable effects on the N1 wave. By contrast, when the synaptic transmission was already conditioned, LFS influenced the synaptic responses oppositely, reducing or annulling the HFS long-term effects. This phenomenon was specifically induced by LFS, because HFS was not able to cause it. The involvement of NMDA receptors in mediating the LFS long-term effects was supported by the fact that AP-5 prevented their induction. In addition, the annulment of HFS long-term effects by LFS was also demonstrated by the shift in the latency of the evoked unitary potentials after LFS. In conclusion, we suggest that the reduction of the previously induced conditioning could represent a cancellation mechanism, useful to quickly adapt the vestibular system to continuous different needs and to avoid saturation.

  8. Porphyrins Fused with Unactivated Polycyclic Aromatic Hydrocarbons

    KAUST Repository

    Diev, Vyacheslav V.; Schlenker, Cody W.; Hanson, Kenneth; Zhong, Qiwen; Zimmerman, Jeramy D.; Forrest, Stephen R.; Thompson, Mark E.

    2012-01-01

    A systematic study of the preparation of porphyrins with extended conjugation by meso,β-fusion with polycyclic aromatic hydrocarbons (PAHs) is reported. The meso-positions of 5,15-unsubstituted porphyrins were readily functionalized with PAHs. Ring fusion using standard Scholl reaction conditions (FeCl 3, dichloromethane) occurs for perylene-substituted porphyrins to give a porphyrin β,meso annulated with perylene rings (0.7:1 ratio of syn and anti isomers). The naphthalene, pyrene, and coronene derivatives do not react under Scholl conditions but are fused using thermal cyclodehydrogenation at high temperatures, giving mixtures of syn and anti isomers of the meso,β-fused porphyrins. For pyrenyl-substituted porphyrins, a thermal method gives synthetically acceptable yields (>30%). Absorption spectra of the fused porphyrins undergo a progressive bathochromic shift in a series of naphthyl (λ max = 730 nm), coronenyl (λ max = 780 nm), pyrenyl (λ max = 815 nm), and perylenyl (λ max = 900 nm) annulated porphyrins. Despite being conjugated with unsubstituted fused PAHs, the β,meso-fused porphyrins are more soluble and processable than the parent nonfused precursors. Pyrenyl-fused porphyrins exhibit strong fluorescence in the near-infrared (NIR) spectral region, with a progressive improvement in luminescent efficiency (up to 13% with λ max = 829 nm) with increasing degree of fusion. Fused pyrenyl-porphyrins have been used as broadband absorption donor materials in photovoltaic cells, leading to devices that show comparatively high photovoltaic efficiencies. © 2011 American Chemical Society.

  9. Porphyrins Fused with Unactivated Polycyclic Aromatic Hydrocarbons

    KAUST Repository

    Diev, Vyacheslav V.

    2012-01-06

    A systematic study of the preparation of porphyrins with extended conjugation by meso,β-fusion with polycyclic aromatic hydrocarbons (PAHs) is reported. The meso-positions of 5,15-unsubstituted porphyrins were readily functionalized with PAHs. Ring fusion using standard Scholl reaction conditions (FeCl 3, dichloromethane) occurs for perylene-substituted porphyrins to give a porphyrin β,meso annulated with perylene rings (0.7:1 ratio of syn and anti isomers). The naphthalene, pyrene, and coronene derivatives do not react under Scholl conditions but are fused using thermal cyclodehydrogenation at high temperatures, giving mixtures of syn and anti isomers of the meso,β-fused porphyrins. For pyrenyl-substituted porphyrins, a thermal method gives synthetically acceptable yields (>30%). Absorption spectra of the fused porphyrins undergo a progressive bathochromic shift in a series of naphthyl (λ max = 730 nm), coronenyl (λ max = 780 nm), pyrenyl (λ max = 815 nm), and perylenyl (λ max = 900 nm) annulated porphyrins. Despite being conjugated with unsubstituted fused PAHs, the β,meso-fused porphyrins are more soluble and processable than the parent nonfused precursors. Pyrenyl-fused porphyrins exhibit strong fluorescence in the near-infrared (NIR) spectral region, with a progressive improvement in luminescent efficiency (up to 13% with λ max = 829 nm) with increasing degree of fusion. Fused pyrenyl-porphyrins have been used as broadband absorption donor materials in photovoltaic cells, leading to devices that show comparatively high photovoltaic efficiencies. © 2011 American Chemical Society.

  10. Mental Illness and Nullity of Marriage: Indian Perspective.

    Science.gov (United States)

    Nambi, Siva; Sarkar, Siddharth

    2015-01-01

    Marriage is a social institution that formalizes and stabilizes the union between a man and wife. At times, either of the parties undergoing the contract of marriage may ask it be declared null and void. Psychiatrists and legal experts may be called in to provide opinion whether such a marriage should be annulled. Some laws in India do state unsoundness of mind as a valid reason for nullity of marriage. However, determining unsoundness of mind can be a difficult issue, especially when made in retrospect. This paper highlights some cases where nullity of marriage was contested in view of unsoundness of mind. Furthermore, some issues encountered by psychiatrists pertaining to nullity of marriage are discussed. Though psychiatrists and legal experts may have different ways of approaching the issue of nullity on the basis of psychiatric disorder, the overall aim of both remains the same of avoiding broken homes, upholding the dignity of the individual and legal framework.

  11. Gold-Catalyzed Formal [4+1]/[4+3] Cycloadditions of Diazo Esters with Triazines.

    Science.gov (United States)

    Zhu, Chenghao; Xu, Guangyang; Sun, Jiangtao

    2016-09-19

    Reported herein is the unprecedented gold-catalyzed formal [4+1]/[4+3] cycloadditions of diazo esters with hexahydro-1,3,4-triazines, thus providing five- and seven-membered heterocycles in moderate to high yields under mild reaction conditions. These reactions feature the use of a gold complex to accomplish the diverse annulations and the first example of the involvement of a gold metallo-enolcarbene in a cycloaddition. It is also the first utilization of stable triazines as formal dipolar adducts in the carbene-involved cycloadditions. Mechanistic investigations reveal that the triazines reacted directly, rather than as formaldimine precursors, in the reaction process. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Microwave assisted highly efficient one-pot multi-component synthesis of novel 2-(tetrasubstituted-1H-pyrrol-3-yl-4H-chroman-4-ones catalyzed by heterogeneous reusable silica gel supported polyphosphoric acid (PPA/SiO2

    Directory of Open Access Journals (Sweden)

    Sumit Kumar

    2018-02-01

    Full Text Available A solvent-free, eco-friendly and facile approach for the synthesis of highly functionalized tetrasubstituted pyrroles has been reported through one-pot four-component reaction of aldehyde, amine, nitroalkane and 1,3-diketone using silica gel supported polyphosphoric acid (PPA–SiO2 under microwave condition. The reaction occured through the in situ formation of β-keto enamine and nitrostyrene analog following Michael addition and finally intramolecular annulation affording the products in good yields. The key features of the present method include clean reaction, mild conditions, low catalyst loading, straightforward, high to excellent yields, short reaction time, avoiding use of harmful metal catalyst and organic solvent, environmentally friendly compared to the existing methods, recovery and reusability of catalyst and easy workup procedure.

  13. Protests put top job for ex-CERN boss in limbo

    Science.gov (United States)

    2008-02-01

    When Luciano Maiani was selected by the Italian government at the end of December to run the country's largest research organization, the National Research Council (CNR), his appointment seemed a formality. His nomination was warmly welcomed by Italian researchers, who believe that his scientific credentials and administrative experience make him the ideal person to try and turn round the demoralized and bureaucratic CNR, and minister for universities and research, Fabio Mussi, extolled his virtues. But as Physics World went to press, Maiani's appointment remained in limbo, with the members of parliament previously expected to rubber stamp the selection putting their decision on hold after discovering that Maiani was one of the 66 letter writers asking for the Pope's visit to be annulled.

  14. Superior Administrative Court of Mannheim. Judgement of March 30, 1982 (Wyhl)

    International Nuclear Information System (INIS)

    Anon.

    1983-01-01

    This publication deals with the decision of March 30, 1982 of the Superior Administrative Court of Mannheim, dismissing the action for annulment of the first part-construction permit for Wyhl nuclear power plant. The publication discusses that part of the Court's statements dealing with the term nuclear installation within the purview of the Atomic Energy Act, section 7, sub-section (1). According to the statement, the term ''nuclear installation for the fission of nuclear fuel'' includes not only that part of an installation where fission takes place but also those components including the surrounding buildings which serve the nuclear purpose of the installation and which thus are subject to the same standards and regulations relating to safety engineering and air pollution control. This definition includes switchgear buildings, reactor auxiliary equipment buildings, the engine house, and cooling water systems including cooling towers. (CB) [de

  15. XSpRES

    DEFF Research Database (Denmark)

    Mainka, Christian; Jensen, Meiko; Iacono, Luigi Lo

    2012-01-01

    XML Encryption and XML Signature are fundamental security standards forming the core for many applications which require to process XML-based data. Due to the increased usage of XML in distributed systems and platforms such as in SOA and Cloud settings, the demand for robust and effective security...... mechanisms increased as well. Recent research work discovered, however, substantial vulnerabilities in these standards as well as in the vast majority of the available implementations. Amongst them, the so-called XML Signature Wrapping attack belongs to the most relevant ones. With the many possible...... instances of this attack type, it is feasible to annul security systems relying on XML Signature and to gain access to protected resources as has been successfully demonstrated lately for various Cloud infrastructures and services. This paper contributes a comprehensive approach to robust and effective XML...

  16. How 'dangerous’ are migrants’ bodies? Narratives about disease and public health and techniques of governance

    Directory of Open Access Journals (Sweden)

    Stojić-Mitrović Marta

    2017-01-01

    Full Text Available In this text I represent the narratives about migrants which are related to their bodies as potential/plausible carriers of diseases that could be spread to local population. The narratives are considered as special manifestations of the discourse of fear, though which migrants are being construed as a form of corporeal security threat. In particular, through the analysis of narratives about ebola and scabies, the potential to use the fear from disease as symbol and instrument of political power is indicated, when a disease ceases to be medical problem and becomes predominantly a social one. Fear from disease and measures undertaken to annul it are thus integrated into techniques of governance. [Project of the Serbian Ministry of Education, Science and Technological Development, Grant no. 177027: Multietnicitet, multikulturalnost, migracije - savremeni procesi

  17. Linear and nonlinear electrostatic modes in a nonuniform magnetized electron plasma

    International Nuclear Information System (INIS)

    Vranjes, J.; Shukla, P.K.; Kono, M.; Poedts, S.

    2001-01-01

    Linear and nonlinear low-frequency modes in a magnetized electron plasma are studied, taking into account a proper description of the equilibrium plasma state that is inhomogeneous. Assuming a homogeneous magnetic field and sheared plasma flows, flute-like perturbations are studied in the presence of density and potential gradients. Linear analysis reveals the presence of a streaming instability and depicts conditions for global linear spiral mode. In the nonlinear domain, a tripolar vortex, which is driven and carried by the flow, is found. Also investigated are the consequences of a magnetic shear as well as nonuniformities along the magnetic field lines, which are shown to be responsible for the possible annulment of the magnetic shear effects. Streaming along the lines of the sheared magnetic field is also studied. A variety of nonlinear structures (viz. global multipolar vortices, local vortex chains, and tripolar vortices) is shown to be the consequence of the simultaneous action of the parallel and perpendicular flows

  18. Biogenetically inspired synthesis and skeletal diversification of indole alkaloids.

    Science.gov (United States)

    Mizoguchi, Haruki; Oikawa, Hideaki; Oguri, Hiroki

    2014-01-01

    To access architecturally complex natural products, chemists usually devise a customized synthetic strategy for constructing a single target skeleton. In contrast, biosynthetic assembly lines often employ divergent intramolecular cyclizations of a polyunsaturated common intermediate to produce diverse arrays of scaffolds. With the aim of integrating such biogenetic strategies, we show the development of an artificial divergent assembly line generating unprecedented numbers of scaffold variations of terpenoid indole alkaloids. This approach not only allows practical access to multipotent intermediates, but also enables systematic diversification of skeletal, stereochemical and functional group properties without structural simplification of naturally occurring alkaloids. Three distinct modes of [4+2] cyclizations and two types of redox-mediated annulations provided divergent access to five skeletally distinct scaffolds involving iboga-, aspidosperma-, andranginine- and ngouniensine-type skeletons and a non-natural variant within six to nine steps from tryptamine. The efficiency of our approach was demonstrated by successful total syntheses of (±)-vincadifformine, (±)-andranginine and (-)-catharanthine.

  19. Hacia una configuración de lugares sin territorios en The Brief Wondrous Life of Oscar Wao

    Directory of Open Access Journals (Sweden)

    Magdalena Lopez

    2015-06-01

    Based on the distinction proposed by Glissant between territory and place, The Brief Wondrous Life of Oscar Wao proposes a fictionalization of the idea of place. The places become are as where the references that “set” territories are decoded and the process of rootlessness of identity categories occurs. However, the categories are not completely annulled. Places respond to an anthropophagic practice in which different territories (geographical, racial, economic, linguistic, sexual, temporal and aesthetic persist, but recycled under a permanent unresolved tension. Such a phenomenon articulates a new form of cultural centerless anthropophagy in the loser character. Oscar is a loser that has been expelled from the logic of the capitalist profit. His symbolic-political recycling does not pretend to erect new territories or binaries rearrangements, but to transform through rootlessness his old territories into the new places.

  20. Complex Algebraic Varieties

    CERN Document Server

    Peternell, Thomas; Schneider, Michael; Schreyer, Frank-Olaf

    1992-01-01

    The Bayreuth meeting on "Complex Algebraic Varieties" focussed on the classification of algebraic varieties and topics such as vector bundles, Hodge theory and hermitian differential geometry. Most of the articles in this volume are closely related to talks given at the conference: all are original, fully refereed research articles. CONTENTS: A. Beauville: Annulation du H(1) pour les fibres en droites plats.- M. Beltrametti, A.J. Sommese, J.A. Wisniewski: Results on varieties with many lines and their applications to adjunction theory.- G. Bohnhorst, H. Spindler: The stability of certain vector bundles on P(n) .- F. Catanese, F. Tovena: Vector bundles, linear systems and extensions of (1).- O. Debarre: Vers uns stratification de l'espace des modules des varietes abeliennes principalement polarisees.- J.P. Demailly: Singular hermitian metrics on positive line bundles.- T. Fujita: On adjoint bundles of ample vector bundles.- Y. Kawamata: Moderate degenerations of algebraic surfaces.- U. Persson: Genus two fibra...