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Sample records for enantioselective iridium catalyzed

  1. Diastereo- and enantioselective iridium-catalyzed allylation of cyclic ketone enolates: synergetic effect of ligands and barium enolates.

    Science.gov (United States)

    Chen, Wenyong; Chen, Ming; Hartwig, John F

    2014-11-12

    We report asymmetric allylic alkylation of barium enolates of cyclic ketones catalyzed by a metallacyclic iridium complex containing a phosphoramidite ligand derived from (R)-1-(2-naphthyl)ethylamine. The reaction products contain adjacent quaternary and tertiary stereocenters. This process demonstrates that unstabilized cyclic ketone enolates can undergo diastereo- and enantioselective Ir-catalyzed allylic substitution reactions with the proper choice of enolate countercation. The products of these reactions can be conveniently transformed to various useful polycarbocyclic structures.

  2. Regio- and Enantioselective N-Allylations of Imidazole, Benzimidazole, and Purine Heterocycles Catalyzed by Single-Component Metallacyclic Iridium Complexes

    Science.gov (United States)

    Stanley, Levi M.

    2010-01-01

    Highly regio- and enantioselective iridium-catalyzed N-allylations of benzimidazoles, imidazoles, and purines have been developed. N-Allylated benzimidazoles and imidazoles were isolated in high yields (up to 97%) with high branched-to-linear selectivity (up to 99:1) and enantioselectivity (up to 98% ee) from the reactions of benzimidazole and imidazole nucleophiles with unsymmetrical allylic carbonates in the presence of single component, ethylene-bound, metallacyclic iridium catalysts. N-Allylated purines were also obtained in high yields (up to 91%) with high N9:N7 selectivity (up to 96:4), high branched-to-linear selectivity (98:2), and high enantioselectivity (up to 98% ee) under similar conditions. The reactions encompass a range of benzimidazole, imidazole, and purine nucleophiles, as well as a variety of unsymmetrical aryl, heteroaryl, and aliphatic allylic carbonates. Competition experiments between common amine nucleophiles and the heterocyclic nitrogen nucleophiles studied in this work illustrate the effect of nucleophile pKa on the rate of iridium-catalyzed N-allylation reactions. Kinetic studies on the allylation of benzimidazole catalyzed by metallacyclic iridium-phosphoramidite complexes, in combination with studies on the deactivation of these catalysts in the presence of heterocyclic nucleophiles, provide insight into the effects of the structure of the phosphoramidite ligands on the stability of the metallacyclic catalysts. The data obtained from these studies has led to the development of N-allylations of benzimidazoles and imidazoles in the absence of an exogenous base. PMID:19480431

  3. Iridium-Catalyzed Asymmetric Intramolecular Allylic Amidation : Enantioselective Synthesis of Chiral Tetrahydroisoquinolines and Saturated Nitrogen Heterocycles

    NARCIS (Netherlands)

    Teichert, Johannes F.; Fañanás-Mastral, Martín; Feringa, Bernard

    2011-01-01

    For the first time iridium catalysis has been used for the synthesis of chiral tetrahydroisoquinolines with excellent yields and high enantioselectivities (see scheme; cod=1,5-cyclooctadiene, DBU=1,8-diazabicyclo[5.4.0]undec-7-ene). These products are important chiral building blocks for the

  4. Application of Phosphine-Phosphite Ligands in the Iridium Catalyzed Enantioselective Hydrogenation of 2-Methylquinoline

    Directory of Open Access Journals (Sweden)

    Miguel Rubio

    2010-10-01

    Full Text Available The hydrogenation of 2-methylquinoline with Ir catalysts based on chiral phosphine-phosphites has been investigated. It has been observed that the reaction is very sensitive to the nature of the ligand. Optimization of the catalyst, allowed by the highly modular structure of these phosphine-phosphites, has improved the enantioselectivity of the reaction up to 73% ee. The influence of additives in this reaction has also been investigated. Contrary to the beneficial influence observed in related catalytic systems, iodine has a deleterious effect in the present case. Otherwise, aryl phosphoric acids produce a positive impact on catalyst activity without a decrease on enantioselectivity.

  5. Enantioselective γ-Alkylation of α,β-Unsaturated Malonates and Ketoesters by a Sequential Ir-Catalyzed Asymmetric Allylic Alkylation/Cope Rearrangement

    OpenAIRE

    Liu, Wen-Bo; Okamoto, Noriko; Alexy, Eric J.; Hong, Allen Y.; Tran, Kristy; Stoltz, Brian M.

    2016-01-01

    A catalytic, enantioselective ? -alkylation of ?,?-unsaturated malonates and ketoesters is reported. This strategy entails a highly regio- and enantioselective iridium-catalyzed ?-alkylation of an extended enolate, and a subsequent translocation of chirality to the ?-position via a Cope rearrangement.

  6. Asymmetric hydrogenation of quinolines catalyzed by iridium complexes of monodentate BINOL-derived phosphoramidites

    NARCIS (Netherlands)

    Mrsic, Natasa; Lefort, Laurent; Boogers, Jeroen A. F.; Minnaard, Adriaan J.; Feringa, Ben L.; de Vries, Johannes G.; Mršić, Nataša

    The monodentate BINOL-derived phosphoramidite PipPhos is used as ligand for the iridium-catalyzed asymmetric hydrogenation of 2- and 2,6-substituted quinolines. If tri-ortho-tolylphosphine and/or chloride salts are used as additives enantioselectivities are strongly enhanced up to 89%. NMR indicates

  7. Enantioselective synthesis of almorexant via iridium-catalysed intramolecular allylic amidation

    NARCIS (Netherlands)

    Fananas Mastral, Martin; Teichert, Johannes F.; Fernandez-Salas, Jose Antonio; Heijnen, Dorus; Feringa, Ben L.

    2013-01-01

    An enantioselective synthesis of almorexant, a potent antagonist of human orexin receptors, is presented. The chiral tetrahydroisoquinoline core structure was prepared via iridium-catalysed asymmetric intramolecular allylic amidation. Further key catalytic steps of the synthesis include an oxidative

  8. Asymmetric Hydrogenation of Quinoxalines Catalyzed by Iridium/PipPhos

    NARCIS (Netherlands)

    Mrsic, Natasa; Jerphagnon, Thomas; Minnaard, Adriaan J.; Feringa, Ben L.; de Vries, Johannes G.

    2009-01-01

    A catalyst made in situ from the (cyclooctadiene)iridium chloride dimer, [Ir(COD)Cl](2), and the monodentate phosphoramidite ligand (S)-PipPhos was used in the enantioselective hydrogenation of 2- and 2,6-substituted quinoxalines. In the presence of piperidine hydrochloride as additive full

  9. Synthesis of benzimidazoles via iridium-catalyzed acceptorless dehydrogenative coupling.

    Science.gov (United States)

    Sun, Xiang; Lv, Xiao-Hui; Ye, Lin-Miao; Hu, Yu; Chen, Yan-Yan; Zhang, Xue-Jing; Yan, Ming

    2015-07-21

    Iridium-catalyzed acceptorless dehydrogenative coupling of tertiary amines and arylamines has been developed. A number of benzimidazoles were prepared in good yields. An iridium-mediated C-H activation mechanism is suggested. This finding represents a novel strategy for the synthesis of benzimidazoles.

  10. Calcium(ii)-catalyzed enantioselective conjugate additions of amines.

    Science.gov (United States)

    Uno, Brice E; Dicken, Rachel D; Redfern, Louis R; Stern, Charlotte M; Krzywicki, Greg G; Scheidt, Karl A

    2018-02-14

    The direct enantioselective chiral calcium(ii)·phosphate complex (Ca[CPA] 2 )-catalyzed conjugate addition of unprotected alkyl amines to maleimides was developed. This mild catalytic system represents a significant advance towards the general convergent asymmetric amination of α,β-unsaturated electrophiles, providing medicinally relevant chiral aminosuccinimide products in high yields and enantioselectivities. Furthermore, the catalyst can be reused directly from a previously chromatographed reaction and still maintain both high yield and selectivity.

  11. Rhodium(II)-catalyzed enantioselective synthesis of troponoids.

    Science.gov (United States)

    Murarka, Sandip; Jia, Zhi-Jun; Merten, Christian; Daniliuc, Constantin-G; Antonchick, Andrey P; Waldmann, Herbert

    2015-06-22

    We report a rhodium(II)-catalyzed highly enantioselective 1,3-dipolar cycloaddition reaction between the carbonyl moiety of tropone and carbonyl ylides to afford troponoids in good to high yields with excellent enantioselectivity. We demonstrate that α-diazoketone-derived carbonyl ylides, in contrast to carbonyl ylides derived from diazodiketoesters, undergo [6+3] cycloaddition reactions with tropone to yield the corresponding bridged heterocycles with excellent stereoselectivity. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Enantioselective Copper-Catalyzed Carboetherification of Unactivated Alkenes**

    Science.gov (United States)

    Bovino, Michael T.; Liwosz, Timothy W.; Kendel, Nicole E.; Miller, Yan; Tyminska, Nina

    2014-01-01

    Chiral saturated oxygen heterocycles are important components of bioactive compounds. Cyclization of alcohols onto pendant alkenes is a direct route to their synthesis, but few catalytic enantioselective methods enabling cyclization onto unactivated alkenes exist. Herein is reported a highly efficient copper-catalyzed cyclization of γ-unsaturated pentenols that terminates in C-C bond formation, a net alkene carboetherification. Both intra- and intermolecular C-C bond formations are demonstrated, yielding functionalized chiral tetrahydrofurans as well as fused-ring and bridged-ring oxabicyclic products. Transition state calculations support a cis-oxycupration stereochemistry-determining step. PMID:24798697

  13. Enantioselective copper-catalyzed carboetherification of unactivated alkenes.

    Science.gov (United States)

    Bovino, Michael T; Liwosz, Timothy W; Kendel, Nicole E; Miller, Yan; Tyminska, Nina; Zurek, Eva; Chemler, Sherry R

    2014-06-16

    Chiral saturated oxygen heterocycles are important components of bioactive compounds. Cyclization of alcohols onto pendant alkenes is a direct route to their synthesis, but few catalytic enantioselective methods enabling cyclization onto unactivated alkenes exist. Herein reported is a highly efficient copper-catalyzed cyclization of γ-unsaturated pentenols which terminates in C-C bond formation, a net alkene carboetherification. Both intra- and intermolecular C-C bond formations are demonstrated, thus yielding functionalized chiral tetrahydrofurans as well as fused-ring and bridged-ring oxabicyclic products. Transition-state calculations support a cis-oxycupration stereochemistry-determining step. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Chemo- and Enantioselective Intramolecular Silver-Catalyzed Aziridinations.

    Science.gov (United States)

    Ju, Minsoo; Weatherly, Cale D; Guzei, Ilia A; Schomaker, Jennifer M

    2017-08-07

    Asymmetric nitrene-transfer reactions are a powerful tool for the preparation of enantioenriched amine building blocks. Reported herein are chemo- and enantioselective silver-catalyzed aminations which transform di- and trisubstituted homoallylic carbamates into [4.1.0]-carbamate-tethered aziridines in good yields and with ee values of up to 92 %. The effects of the substrate, silver counteranion, ligand, solvent, and temperature on both the chemoselectivity and ee value were explored. Stereochemical models were proposed to rationalize the observed absolute stereochemistry of the aziridines, which undergo nucleophilic ring opening to yield enantioenriched amines with no erosion in stereochemical integrity. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Asymmetric Synthesis of Optically Active Spirocyclic Indoline Scaffolds through an Enantioselective Reduction of Indoles

    KAUST Repository

    Borrmann, Ruediger; Knop, Nils; Rueping, Magnus

    2016-01-01

    An enantioselective synthesis of spirocyclic indoline scaffolds was achieved by applying an asymmetric iridium-catalyzed hydrogenation of 3H-indoles. Low catalyst loadings and mild reaction conditions provide a broad range of differently substituted

  16. 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

  17. 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.

  18. Iridium/Bipyridine-Catalyzed ortho-Selective C-H Borylation of Phenol and Aniline Derivatives.

    Science.gov (United States)

    Li, Hong-Liang; Kanai, Motomu; Kuninobu, Yoichiro

    2017-11-03

    An iridium-catalyzed ortho-selective C-H borylation of phenol and aniline derivatives has been successfully developed. Iridium/bipyridine-catalyzed C-H borylation generally occurred at the meta- and para-positions of aromatic substrates. Introduction of an electron-withdrawing substituent on the bipyridine-type ligand and a methylthiomethyl group on the hydroxy and amino groups of the phenol and aniline substrates, however, dramatically altered the regioselectivity, affording exclusively ortho-borylated products. The reaction proceeded in good to excellent yields with good functional group tolerance. C-H borylation was applied to the synthesis of a calcium receptor modulator.

  19. Synthesis of Fluoroalkoxy Substituted Arylboronic Esters by Iridium-Catalyzed Aromatic C–H Borylation

    KAUST Repository

    Batool, Farhat

    2015-08-17

    The preparation of fluoroalkoxy arylboronic esters by iridium-catalyzed aromatic C–H borylation is described. The fluoroalkoxy groups employed include trifluoromethoxy, difluoromethoxy, 1,1,2,2-tetrafluoroethoxy, and 2,2-difluoro-1,3-benzodioxole. The borylation reactions were carried out neat without the use of a glovebox or Schlenk line. The regioselectivities available through the iridium-catalyzed C–H borylation are complementary to those obtained by the electrophilic aromatic substitution reactions of fluoroalkoxy arenes. Fluoroalkoxy arylboronic esters can serve as versatile building blocks.

  20. Synthesis of Fluoroalkoxy Substituted Arylboronic Esters by Iridium-Catalyzed Aromatic C–H Borylation

    KAUST Repository

    Batool, Farhat; Parveen, Shehla; Emwas, Abdul-Hamid M.; Sioud, Salim; Gao, Xin; Munawar, Munawar A.; Chotana, Ghayoor A.

    2015-01-01

    The preparation of fluoroalkoxy arylboronic esters by iridium-catalyzed aromatic C–H borylation is described. The fluoroalkoxy groups employed include trifluoromethoxy, difluoromethoxy, 1,1,2,2-tetrafluoroethoxy, and 2,2-difluoro-1,3-benzodioxole. The borylation reactions were carried out neat without the use of a glovebox or Schlenk line. The regioselectivities available through the iridium-catalyzed C–H borylation are complementary to those obtained by the electrophilic aromatic substitution reactions of fluoroalkoxy arenes. Fluoroalkoxy arylboronic esters can serve as versatile building blocks.

  1. Pd(II)-Catalyzed Enantioselective C-H Olefination of Diphenylacetic Acids

    Science.gov (United States)

    Shi, Bing-Feng; Zhang, Yang-Hui; Lam, Jonathan K.; Wang, Dong-Hui; Yu, Jin-Quan

    2009-01-01

    Pd(II)-catalyzed enantioselective C-H olefination of diphenylacetic acid substrates has been achieved through the use of mono-protected chiral amino acid ligands. The absolute configuration of the resulting olefinated products is consistent with that of a proposed C-H insertion intermediate. PMID:20017549

  2. Enantioselective Evans-Tishchenko Reduction of b-Hydroxyketone Catalyzed by Lithium Binaphtholate

    Directory of Open Access Journals (Sweden)

    Makoto Nakajima

    2011-06-01

    Full Text Available Lithium diphenylbinaphtholate catalyzed the enantioselective Evans-Tishchenko reduction of achiral b-hydroxyketones to afford monoacyl-protected 1,3-diols with high stereoselectivities. In the reaction of racemic b-hydroxyketones, kinetic optical resolution occurred in a highly stereoselective manner.

  3. Enantioselective Copper-Catalyzed Oxy-Alkynylation of Diazo Compounds.

    Science.gov (United States)

    Hari, Durga Prasad; Waser, Jerome

    2017-06-28

    Enantioselective catalytic methods allowing the addition of both a nucleophile and an electrophile onto diazo compounds give a fast access into important building blocks. Herein, we report the highly enantioselective oxyalkynylation of diazo compounds using ethynylbenziodoxol-(on)e reagents and a simple copper bisoxazoline catalyst. The obtained α-benzoyloxy propargylic esters are useful building blocks, which are difficult to synthesize in enantiopure form using other methods. The obtained products could be efficiently transformed into vicinal diols and α-hydroxy propargylic esters without loss in enantiopurity.

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

    KAUST Repository

    Ma, Ting

    2011-03-09

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

  5. Guanidine-catalyzed enantioselective desymmetrization of meso-aziridines

    KAUST Repository

    Zhang, Yan

    2011-01-01

    An amino-indanol derived chiral guanidine was developed as an efficient Brønsted base catalyst for the desymmetrization of meso-aziridines with both thiols and carbamodithioic acids as nucleophiles, which provided 1,2-difunctionalized ring-opened products in high yields and enantioselectivities. © The Royal Society of Chemistry.

  6. 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.

  7. Experimental and Theoretical Mechanistic Investigation of the Iridium-Catalyzed Dehydrogenative Decarbonylation of Primary Alcohols

    DEFF Research Database (Denmark)

    Olsen, Esben Paul Krogh; Singh, Thishana; Harris, Pernille

    2015-01-01

    The mechanism for the iridium-BINAP catalyzed dehydrogenative decarbonylation of primary alcohols with the liberation of molecular hydrogen and carbon monoxide was studied experimentally and computationally. The reaction takes place by tandem catalysis through two catalytic cycles involving...... cycles. One carbon monoxide ligand was shown to remain coordinated to iridium throughout the reaction, and release of carbon monoxide was suggested to occur from a dicarbonyl complex. IrH2Cl(CO)(rac-BINAP) was also synthesized and detected in the dehydrogenation of benzyl alcohol. In the same experiment......, IrHCl2(CO)(rac-BINAP) was detected from the release of HCl in the dehydrogenation and subsequent reaction with IrCl(CO)(rac-BINAP). This indicated a substitution of chloride with the alcohol to form a square planar iridium alkoxo complex that could undergo a beta-hydride elimination. A KIE of 1...

  8. Iridium catalyzed growth of vertically aligned CNTs by APCVD

    International Nuclear Information System (INIS)

    Sahoo, R.K.; Jacob, C.

    2014-01-01

    Highlights: • Growth of uniform-diameter vertically-aligned multi-walled CNTs by APCVD. • Use of high melting point low carbon solubility iridium nanoparticles as catalyst. • Optimization of growth time for uniform sized, uniformly aligned CNTs. • Growth model for the various features in the vertically aligned CNTs is proposed. - Abstract: Vertically aligned carbon nanotubes (VA-CNTs) have been synthesized using high temperature catalyst nanoparticles of iridium. The catalyst layer was prepared by DC sputtering. Particle density, circularity and average particle size of the catalyst were analyzed using field emission scanning electron microscopy. The alignment, morphology and the length of the as-grown CNTs were analyzed using field-emission scanning electron microscopy. High resolution transmission electron microscopy was carried out to observe the layers of graphitic stacking which form the carbon nanotubes. Micro Raman measurement was used for the analysis of the graphitic crystallinity of the as-grown carbon nano structures. Effects of growth time variation on growth morphology and alignment have been studied. The alignment has been explained on the basis of the crowding effect of the neighboring nanoparticles

  9. Iridium catalyzed growth of vertically aligned CNTs by APCVD

    Energy Technology Data Exchange (ETDEWEB)

    Sahoo, R.K.; Jacob, C., E-mail: cxj14_holiday@yahoo.com

    2014-07-01

    Highlights: • Growth of uniform-diameter vertically-aligned multi-walled CNTs by APCVD. • Use of high melting point low carbon solubility iridium nanoparticles as catalyst. • Optimization of growth time for uniform sized, uniformly aligned CNTs. • Growth model for the various features in the vertically aligned CNTs is proposed. - Abstract: Vertically aligned carbon nanotubes (VA-CNTs) have been synthesized using high temperature catalyst nanoparticles of iridium. The catalyst layer was prepared by DC sputtering. Particle density, circularity and average particle size of the catalyst were analyzed using field emission scanning electron microscopy. The alignment, morphology and the length of the as-grown CNTs were analyzed using field-emission scanning electron microscopy. High resolution transmission electron microscopy was carried out to observe the layers of graphitic stacking which form the carbon nanotubes. Micro Raman measurement was used for the analysis of the graphitic crystallinity of the as-grown carbon nano structures. Effects of growth time variation on growth morphology and alignment have been studied. The alignment has been explained on the basis of the crowding effect of the neighboring nanoparticles.

  10. Sterically directed iridium-catalyzed hydrosilylation of alkenes in the presence of alkynes.

    Science.gov (United States)

    Muchnij, Jill A; Kwaramba, Farai B; Rahaim, Ronald J

    2014-03-07

    A selective iridium catalyzed hydrosilylation of alkenes in the presence of more reactive alkynes is described. By utilizing [IrCl(COD)]2 in the presence of excess COD, hydrosilylation of alkenes and alkynes with ethynylsilanes is achieved with good chemo- and regioselectivity. This approach goes against the traditional reactivity trends of platinum and rhodium catalysts and allows access to highly substituted silicon alkyne tethers.

  11. 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.

  12. Lipase-catalyzed highly enantioselective kinetic resolution of boron-containing chiral alcohols.

    Science.gov (United States)

    Andrade, Leandro H; Barcellos, Thiago

    2009-07-16

    The first application of enzymes as catalysts to obtain optically pure boron compounds is described. The kinetic resolution of boron-containing chiral alcohols via enantioselective transesterification catalyzed by lipases was studied. Aromatic, allylic, and aliphatic secondary alcohols containing a boronate ester or boronic acid group were resolved by lipase from Candida antartica (CALB), and excellent E values (E > 200) and high enantiomeric excesses (up to >99%) of both remaining substrates and acetylated product were obtained.

  13. Lewis base catalyzed enantioselective allylic hydroxylation of Morita-Baylis-Hillman carbonates with water

    KAUST Repository

    Zhu, Bo

    2011-08-19

    A Lewis base catalyzed allylic hydroxylation of Morita-Baylis-Hillman (MBH) carbonates has been developed. Various chiral MBH alcohols can be synthesized in high yields (up to 99%) and excellent enantioselectivities (up to 94% ee). This is the first report using water as a nucleophile in asymmetric organocatalysis. The nucleophilic role of water has been verified using 18O-labeling experiments. © 2011 American Chemical Society.

  14. Rhodium-catalyzed chemo-, regio-, and enantioselective addition of 2-pyridones to terminal allenes.

    Science.gov (United States)

    Li, Changkun; Kähny, Matthias; Breit, Bernhard

    2014-12-08

    A rhodium-catalyzed chemo-, regio-, and enantioselective addition of 2-pyridones to terminal allenes to give branched N-allyl 2-pyridones is reported. Preliminary mechanistic studies support the hypothesis that the reaction was initiated from the more acidic 2-hydroxypyridine form, and the initial kinetic O-allylation product was finally converted into the thermodynamically more stable N-allyl 2-pyridones. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. An iron/amine-catalyzed cascade process for the enantioselective functionalization of allylic alcohols.

    Science.gov (United States)

    Quintard, Adrien; Constantieux, Thierry; Rodriguez, Jean

    2013-12-02

    Three is a lucky number: An enantioselective transformation of allylic alcohols into β-chiral saturated alcohols has been developed by combining two distinct metal- and organocatalyzed catalytic cycles. This waste-free triple cascade process merges an iron-catalyzed borrowing-hydrogen step with an aminocatalyzed nucleophilic addition reaction. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Enantioselective Intramolecular CH-Insertions upon Cu-Catalyzed Decomposition of Phenyliodonium Ylides

    Directory of Open Access Journals (Sweden)

    Christelle Boléa

    2001-02-01

    Full Text Available The Cu-catalyzed intramolecular CH insertion of phenyliodonium ylide 5b has been investigated at 0° C in the presence of several chiral ligands. Enantioselectivities vary in the range of 38–72 %, and are higher than those resulting from reaction of the diazo compound 5c at 65° C. The results are consistent with a carbenoid mechanism for Cu-catalyzed decomposition of phenyliodonium ylides.

  17. Enantioselective synthesis of chiral 3-aryl-1-indanones through rhodium-catalyzed asymmetric intramolecular 1,4-addition.

    Science.gov (United States)

    Yu, Yue-Na; Xu, Ming-Hua

    2013-03-15

    Enantioselective synthesis of potentially useful chiral 3-aryl-1-indanones was achieved through a rhodium-catalyzed asymmetric intramolecular 1,4-addition of pinacolborane chalcone derivatives using extraordinary simple MonoPhos as chiral ligand under relatively mild conditions. This novel protocol offers an easy access to a wide variety of enantioenriched 3-aryl-1-indanone derivatives in high yields (up to 95%) with excellent enantioselectivities (up to 95% ee).

  18. Hydrogen transfer reduction of polyketones catalyzed by iridium complexes: a novel route towards more biocompatible materials.

    Science.gov (United States)

    Milani, Barbara; Crottib, Corrado; Farnetti, Erica

    2008-09-14

    Transfer hydrogenation from 2-propanol to CO/4-methylstyrene and CO/styrene polyketones was catalyzed by [Ir(diene)(N-N)X] (N-N = nitrogen chelating ligand; X = halogen) in the presence of a basic cocatalyst. The reactions were performed using dioxane as cosolvent, in order to overcome problems due to low polyketone solubility. The polyalcohols were obtained in yields up to 95%, the conversions being markedly dependent on the nature of the ligands coordinated to iridium as well as on the experimental conditions.

  19. Lewis Base Activation of Silyl Acetals: Iridium-Catalyzed Reductive Horner-Wadsworth-Emmons Olefination.

    Science.gov (United States)

    Dakarapu, Udaya Sree; Bokka, Apparao; Asgari, Parham; Trog, Gabriela; Hua, Yuanda; Nguyen, Hiep H; Rahman, Nawal; Jeon, Junha

    2015-12-04

    A Lewis base promoted deprotonative pronucleophile addition to silyl acetals has been developed and applied to the iridium-catalyzed reductive Horner-Wadsworth-Emmons (HWE) olefination of esters and the chemoselective reduction of the resulting enoates. Lewis base activation of silyl acetals generates putative pentacoordinate silicate acetals, which fragment into aldehydes, silanes, and alkoxides in situ. Subsequent deprotonative metalation of phosphonate esters followed by HWE with aldehydes furnishes enoates. This operationally convenient, mechanistically unique protocol converts the traditionally challenging aryl, alkenyl, and alkynyl esters to homologated enoates at room temperature within a single vessel.

  20. Design, Synthesis and Biological Activity of Novel Reversible Peptidyl FVIIa Inhibitors Rh-Catalyzed Enantioselective Synthesis of Diaryl Amines

    DEFF Research Database (Denmark)

    Storgaard, Morten

    functional group tolerance. Unfortunately, these -aryl tetramic acids were too unreactive and ring opening toward the synthesis of the building block did not succeed. However, -aryl tetramic acids are still interesting compounds due to their potential biological activity. The building block 3.15 (P1......-catalyzed enantioselective synthesis of diaryl amines, which is an important class of compounds (Chapter 4). For example it is found in the third generation anti-histaminic agent levocetirizine. Development of efficient synthetic routes is therefore of considerably interest. The rhodium-catalyzed enantioselective synthesis...

  1. Asymmetric Synthesis of Optically Active Spirocyclic Indoline Scaffolds through an Enantioselective Reduction of Indoles

    KAUST Repository

    Borrmann, Ruediger

    2016-11-30

    An enantioselective synthesis of spirocyclic indoline scaffolds was achieved by applying an asymmetric iridium-catalyzed hydrogenation of 3H-indoles. Low catalyst loadings and mild reaction conditions provide a broad range of differently substituted products with excellent yields and enantioselectivities. The developed methodology allows an efficient synthesis of this important spirocyclic structural motif, which is present in numerous biologically active molecules and privileged structures in medicinal chemistry.

  2. Cyclic aldimines as superior electrophiles for Cu-catalyzed decarboxylative Mannich reaction of β-ketoacids with a broad scope and high enantioselectivity.

    Science.gov (United States)

    Zhang, Heng-Xia; Nie, Jing; Cai, Hua; Ma, Jun-An

    2014-05-02

    A novel Cu-catalyzed enantioselective decarboxylative Mannich reaction of cyclic aldimines with β-ketoacids is described. The cyclic structure of these aldimines, in which the C═N bond is constrained in the Z geometry, appears to be important, allowing Mannich condensation to proceed in high yields with excellent enantioselectivities. A chiral chroman-4-amine was synthesized from the decarboxylative Mannich product in several steps without loss of enantioselectivity.

  3. Rhodium-catalyzed enantioselective intramolecular C-H silylation for the syntheses of planar-chiral metallocene siloles.

    Science.gov (United States)

    Zhang, Qing-Wei; An, Kun; Liu, Li-Chuan; Yue, Yuan; He, Wei

    2015-06-01

    Reported herein is the rhodium-catalyzed enantioselective C-H bond silylation of the cyclopentadiene rings in Fe and Ru metallocenes. Thus, in the presence of (S)-TMS-Segphos, the reactions took place under very mild conditions to afford metallocene-fused siloles in good to excellent yields and with ee values of up to 97%. During this study it was observed that the steric hindrance of chiral ligands had a profound influence on the reactivity and enantioselectivity of the reaction, and might hold the key to accomplishing conventionally challenging asymmetric C-H silylations. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Bicyclic Guanidine Catalyzed Asymmetric Tandem Isomerization Intramolecular-Diels-Alder Reaction: The First Catalytic Enantioselective Total Synthesis of (+)-alpha-Yohimbine.

    Science.gov (United States)

    Feng, Wei; Jiang, Danfeng; Kee, Choon-Wee; Liu, Hongjun; Tan, Choon-Hong

    2016-02-04

    Hydroisoquinoline derivatives were prepared in moderate to good enantioselectivities via a bicyclic guanidine-catalyzed tandem isomerization intramolecular-Diels-Alder (IMDA) reaction of alkynes. With this synthetic method, the first enantioselective synthesis of (+)-alpha-yohimbine was completed in 9 steps from the IMDA products. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Highly enantioselective rhodium(I)-catalyzed carbonyl carboacylations initiated by C-C bond activation.

    Science.gov (United States)

    Souillart, Laetitia; Cramer, Nicolai

    2014-09-01

    The lactone motif is ubiquitous in natural products and pharmaceuticals. The Tishchenko disproportionation of two aldehydes, a carbonyl hydroacylation, is an efficient and atom-economic access to lactones. However, these reaction types are limited to the transfer of a hydride to the accepting carbonyl group. The transfer of alkyl groups enabling the formation of CC bonds during the ester formation would be of significant interest. Reported herein is such asymmetric carbonyl carboacylation of aldehydes and ketones, thus affording complex bicyclic lactones in excellent enantioselectivities. The rhodium(I)-catalyzed transformation is induced by an enantiotopic CC bond activation of a cyclobutanone and the formed rhodacyclic intermediate reacts with aldehyde or ketone groups to give highly functionalized lactones. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Asymmetric synthesis of allylic sulfonic acids: enantio- and regioselective iridium-catalyzed allylations of Na2SO3.

    Science.gov (United States)

    Liu, Wei; Zhao, Xiao-ming; Zhang, Hong-bo; Zhang, Liang; Zhao, Ming-zhu

    2014-12-15

    An enantioselective allylation reaction of allylic carbonates with sodium sulfite (Na2 SO3 ) catalyzed by Ir complex was accomplished, providing allylic sulfonic acids in good to excellent yields with a high level of enantio- and regioselectivities. (R)-2-Phenyl-2-sulfoacetic acid, a key intermediate for the synthesis of Cefsulodin and Sulbenicillin, was synthesized as well. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Regioconvergent and Enantioselective Rhodium-Catalyzed Hydroamination of Internal and Terminal Alkynes: A Highly Flexible Access to Chiral Pyrazoles.

    Science.gov (United States)

    Haydl, Alexander M; Hilpert, Lukas J; Breit, Bernhard

    2016-05-04

    The rhodium-catalyzed asymmetric N-selective coupling of pyrazole derivatives with internal and terminal alkynes features an utmost chemo-, regio-, and enantioselective access to enantiopure allylic pyrazoles, readily available for incorporation in small-molecule pharmaceuticals. This methodology is distinguished by a broad substrate scope, resulting in a remarkable compatability with a variety of different functional groups. It furthermore exhibits an intriguing case of regio-, position-, and enantioselectivity in just one step, underscoring the sole synthesis of just one out of up to six possible products in a highly flexible approach to allylated pyrazoles by emanating from various internal and terminal alkynes. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Regio-, Diastereo-, and Enantioselective Nitroso-Diels-Alder Reaction of 1,3-Diene-1-carbamates Catalyzed by Chiral Phosphoric Acids.

    Science.gov (United States)

    Pous, Jonathan; Courant, Thibaut; Bernadat, Guillaume; Iorga, Bogdan I; Blanchard, Florent; Masson, Géraldine

    2015-09-23

    Chiral phosphoric acid-catalyzed asymmetric nitroso-Diels-Alder reaction of nitrosoarenes with carbamate-dienes afforded cis-3,6-disubstituted dihydro-1,2-oxazines in high yields with excellent regio-, diastereo-, and enantioselectivities. Interestingly, we observed that the catalyst is able not only to control the enantioselectivity but also to reverse the regioselectivity of the noncatalyzed nitroso-Diels-Alder reaction. The regiochemistry reversal and asynchronous concerted mechanism were confirmed by DFT calculations.

  9. Copper(II)-catalyzed exo and enantioselective cycloadditions of azomethine imines.

    Science.gov (United States)

    Sibi, Mukund P; Rane, Digamber; Stanley, Levi M; Soeta, Takahiro

    2008-07-17

    A strategy for exo and enantioselective 1,3-dipolar cycloaddition of azomethine imines to 2-acryloyl-3-pyrazolidinone is described. The corresponding cycloadducts are isolated with high diastereoselectivities (up to >96:4 exo/endo) and enantioselectivities (up to 98% ee).

  10. Iridium-Catalyzed Condensation of Primary Amines To Form Secondary Amines

    DEFF Research Database (Denmark)

    Lorentz-Petersen, Linda Luise Reeh; Jensen, Paw; Madsen, Robert

    2009-01-01

    Symmetric secondary amines are readily obtained by heating a neat primary amine with 0.5 mol% of bis(dichloro[eta(5)-pentamethylcyclopentadienyl]iridium). The products are isolated by direct distillation in good yields.......Symmetric secondary amines are readily obtained by heating a neat primary amine with 0.5 mol% of bis(dichloro[eta(5)-pentamethylcyclopentadienyl]iridium). The products are isolated by direct distillation in good yields....

  11. 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.

  12. Highly Enantioselective Rhodium-Catalyzed Addition of Arylboroxines to Simple Aryl Ketones: Efficient Synthesis of Escitalopram.

    Science.gov (United States)

    Huang, Linwei; Zhu, Jinbin; Jiao, Guangjun; Wang, Zheng; Yu, Xingxin; Deng, Wei-Ping; Tang, Wenjun

    2016-03-24

    Highly enantioselective additions of arylboroxines to simple aryl ketones have been achieved for the first time with a Rh/(R,R,R,R)-WingPhos catalyst, thus providing a range of chiral diaryl alkyl carbinols with excellent ee values and yields. (R,R,R,R)-WingPhos has been proven to be crucial for the high reactivity and enantioselectivity. The method has enabled a new, concise, and enantioselective synthesis of the antidepressant drug escitalopram. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Nickel-catalyzed regio- and enantioselective aminolysis of 3,4-epoxy alcohols.

    Science.gov (United States)

    Wang, Chuan; Yamamoto, Hisashi

    2015-04-08

    The first catalytic regio- and enantioselective aminolysis of 3,4-epoxy alcohols has been accomplished. Under the catalysis of Ni(ClO4)2·6H2O, the C4 selective ring opening of various 3,4-epoxy alcohols proceeded in a stereospecific manner with high regioselectivities. Furthermore, with the Ni-BINAM catalytic system the enantioselective ring opening of 3,4-epoxy alcohols furnished various γ-hydroxy-δ-amino alcohols as products with complete regiocontrol and high enantioselectivities (up to 94% ee).

  14. Rhodium-Catalyzed Enantioselective Cyclopropanation of Olefins with N-Sulfonyl 1,2,3-Triazoles

    Science.gov (United States)

    Chuprakov, Stepan; Kwok, Sen Wai; Zhang, Li; Lercher, Lukas; Fokin, Valery V.

    2009-01-01

    N-Sulfonyl 1,2,3-triazoles readily form rhodium(II) azavinyl carbenes, which react with olefins to produce cyclopropanes with excellent diastereo- and enantioselectivity and in high yield. PMID:19928917

  15. Enantioselective Addition of Allyltin Reagents to Amino Aldehydes Catalyzed with Bis(oxazolinylphenylrhodium(III Aqua Complexes

    Directory of Open Access Journals (Sweden)

    Hisao Nishiyama

    2011-06-01

    Full Text Available Bis(oxazolinylphenylrhodium(III aqua complexes, (PheboxRhX2(H2O [X = Cl, Br], were found to be efficient Lewis acid catalysts for the enantioselective addition of allyl- and methallyltributyltin reagents to amino aldehydes. The reactions proceed smoothly in the presence of 5–10 mol % of (PheboxRhX2(H2O complex at ambient temperature to give the corresponding amino alcohols with modest to good enantioselectivity (up to 94% ee.

  16. Theoretical study on the reaction mechanisms of Michael chirality addition between propionaldehyde and nitroalkene catalyzed by an enantioselective catalyst.

    Science.gov (United States)

    Zhou, Xinming; Li, Ling; Sun, Xuejun; Wang, Yajun; Du, Dongmei; Fu, Hui

    2018-06-01

    The asymmetric Michael addition between propionaldehyde and nitroalkene catalyzed by 8-(ethoxycarbonyl)-1,2,3,3a,8,8a-hexahydropyrrolo[2,3-b]indole-2-carboxylic acid has obtained relatively high yields and excellent enantioselectivities at room temperature. In this study, the molecular structures and optical activity of the most stable conformation I are optimized at B3LYP/6-311++ G(d,p) level. We find that levorotatory conformation I catalyzing the same Michael addition can produce laevo-product A and dextrorotatory conformation I' can obtain the dextral-product A'. These results have guiding significance for further studying on the new chemzymes and the mechanism of the obtained different chiral products. © 2018 Wiley Periodicals, Inc.

  17. Syntheses of the hexahydroindene cores of indanomycin and stawamycin by combinations of iridium-catalyzed asymmetric allylic alkylations and intramolecular Diels-Alder reactions.

    Science.gov (United States)

    Gärtner, Martin; Satyanarayana, Gedu; Förster, Sebastian; Helmchen, Günter

    2013-01-02

    Short and concise syntheses of the hexahydroindene cores of the antibiotics indanomycin (X-14547 A) and stawamycin are presented. Key methods used are an asymmetric iridium-catalyzed allylic alkylation, a modified Julia olefination, a Suzuki-Miyaura coupling, and an intramolecular Diels-Alder reaction. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Stereospecific nickel-catalyzed cross-coupling reactions of alkyl ethers: enantioselective synthesis of diarylethanes.

    Science.gov (United States)

    Taylor, Buck L H; Swift, Elizabeth C; Waetzig, Joshua D; Jarvo, Elizabeth R

    2011-01-26

    Secondary benzylic ethers undergo stereospecific substitution reactions with Grignard reagents in the presence of nickel catalysts. Reactions proceed with inversion of configuration and high stereochemical fidelity. This reaction allows for facile enantioselective synthesis of biologically active diarylethanes from readily available optically enriched carbinols.

  19. Uncovering Key Structural Features of an Enantioselective Peptide-Catalyzed Acylation Utilizing Advanced NMR Techniques

    Czech Academy of Sciences Publication Activity Database

    Procházková, Eliška; Kolmer, A.; Ilgen, J.; Schwab, M.; Kaltschnee, L.; Fredersdorf, M.; Schmidts, V.; Wende, R. C.; Schreiner, P. R.; Thiele, C. M.

    2016-01-01

    Roč. 55, č. 51 (2016), s. 15754-15759 ISSN 1433-7851 Institutional support: RVO:61388963 Keywords : conformational analysis * enantioselective acylations * NMR spectroscopy * pure shift NMR * RDCs Subject RIV: CC - Organic Chemistry Impact factor: 11.994, year: 2016

  20. Asymmetric Hydrogenation of Seven-Membered C=N-containing Heterocycles and Rationalization of the Enantioselectivity.

    Science.gov (United States)

    Balakrishna, Bugga; Bauzá, Antonio; Frontera, Antonio; Vidal-Ferran, Anton

    2016-07-18

    Iridium(I) complexes with phosphine-phosphite ligands efficiently catalyze the enantioselective hydrogenation of diverse seven-membered C=N-containing heterocyclic compounds (eleven examples; up to 97 % ee). The P-OP ligand L3, which incorporates an ortho-diphenyl substituted octahydrobinol phosphite fragment, provided the highest enantioselectivities in the hydrogenation of most of the heterocyclic compounds studied. The observed stereoselection was rationalized by means of DFT calculations. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Copper(II)-catalyzed enantioselective hydrosilylation of halo-substituted alkyl aryl and heteroaryl ketones: asymmetric synthesis of (R)-fluoxetine and (S)-duloxetine.

    Science.gov (United States)

    Zhou, Ji-Ning; Fang, Qiang; Hu, Yi-Hu; Yang, Li-Yao; Wu, Fei-Fei; Xie, Lin-Jie; Wu, Jing; Li, Shijun

    2014-02-14

    A set of reaction conditions has been established to facilitate the non-precious copper-catalyzed enantioselective hydrosilylation of a number of structurally diverse β-, γ- or ε-halo-substituted alkyl aryl ketones and α-, β- or γ-halo-substituted alkyl heteroaryl ketones under air to afford a broad spectrum of halo alcohols in high yields and good to excellent enantioselectivities (up to 99% ee). The developed procedure has been successfully applied to the asymmetric synthesis of antidepressant drugs (R)-fluoxetine and (S)-duloxetine, which highlighted its synthetic utility.

  2. Ultrasound-Assisted Enantioselective Esterification of Ibuprofen Catalyzed by a Flower-Like Nanobioreactor

    Directory of Open Access Journals (Sweden)

    Baiyi An

    2016-04-01

    Full Text Available A flower-like nanobioreactor was prepared for resolution of ibuprofen in organic solvents. Ultrasound irradiation has been used to improve the enzyme performance of APE1547 (a thermophilic esterase from the archaeon Aeropyrum pernix K1 in the enantioselective esterification. Under optimum reaction conditions (ultrasound power, 225 W; temperature, 45 °C; water activity, 0.21, the immobilized APE1547 showed an excellent catalytic performance (enzyme activity, 13.26 μmol/h/mg; E value, 147.1. After ten repeated reaction batches, the nanobioreactor retained almost 100% of its initial enzyme activity and enantioselectivity. These results indicated that the combination of the immobilization method and ultrasound irradiation can enhance the enzyme performance dramatically.

  3. Continuous-flow enantioselective α-aminoxylation of aldehydes catalyzed by a polystyrene-immobilized hydroxyproline

    Directory of Open Access Journals (Sweden)

    Xacobe C. Cambeiro

    2011-10-01

    Full Text Available The application of polystyrene-immobilized proline-based catalysts in packed-bed reactors for the continuous-flow, direct, enantioselective α-aminoxylation of aldehydes is described. The system allows the easy preparation of a series of β-aminoxy alcohols (after a reductive workup with excellent optical purity and with an effective catalyst loading of ca. 2.5% (four-fold reduction compared to the batch process working at residence times of ca. 5 min.

  4. Copper(II)/amine synergistically catalyzed enantioselective alkylation of cyclic N-acyl hemiaminals with aldehydes.

    Science.gov (United States)

    Sun, Shutao; Mao, Ying; Lou, Hongxiang; Liu, Lei

    2015-07-07

    The first catalytic asymmetric alkylation of N-acyl quinoliniums with aldehydes has been described. A copper/amine synergistic catalytic system has been developed, allowing the addition of functionalized aldehydes to a wide range of electronically varied N-acyl quinoliniums in good yields with excellent enantiocontrol. The synergistic catalytic system was also effective for N-acyl dihydroisoquinoliniums and β-caboliniums, demonstrating the general applicability of the protocol in the enantioselective alkylation of diverse cyclic N-acyl hemiaminals.

  5. 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.

  6. Chiral Nickel(II) Complex Catalyzed Enantioselective Doyle-Kirmse Reaction of α-Diazo Pyrazoleamides.

    Science.gov (United States)

    Lin, Xiaobin; Tang, Yu; Yang, Wei; Tan, Fei; Lin, Lili; Liu, Xiaohua; Feng, Xiaoming

    2018-03-07

    Although high enantioselectivity of [2,3]-sigmatropic rearrangement of sulfonium ylides (Doyle-Kirmse reaction) has proven surprisingly elusive using classic chiral Rh(II) and Cu(I) catalysts, in principle it is due to the difficulty in fine discrimination of the heterotopic lone pairs of sulfur and chirality inversion at sulfur of sulfonium ylides. Here, we show that the synergistic merger of new α-diazo pyrazoleamides and a chiral N, N'-dioxide-nickel(II) complex catalyst enables a highly enantioselective Doyle-Kirmse reaction. The pyrazoleamide substituent serves as both an activating and a directing group for the ready formation of a metal-carbene- and Lewis-acid-bonded ylide intermediate in the assistance of a dual-tasking nickel(II) complex. An alternative chiral Lewis-acid-bonded ylide pathway greatly improves the product enantiopurity even for the reaction of a symmetric diallylsulfane. The majority of transformations over a series of aryl- or vinyl-substituted α-diazo pyrazoleamindes and sulfides proceed rapidly (within 5-20 min in most cases) with excellent results (up to 99% yield and 96% ee), providing a breakthrough in enantioselective Doyle-Kirmse reaction.

  7. Enantioselective conjugate addition of diethylzinc to chalcone catalyzed by Co(acac)2 and chiral amino alcohols

    NARCIS (Netherlands)

    Vries, André H.M. de; Feringa, Bernard

    1997-01-01

    Co(acac)2 in the presence of chiral ligands has been employed as catalyst for the enantioselective conjugate addition of diethylzinc to chalcone. With chiral amino alcohols derived from (+)-camphor, enantioselectivities up to 83% were achieved.

  8. 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.

  9. Vanadium-Catalyzed Enantioselective Desymmetrization of meso-Secondary Allylic Alcohols and Homoallylic Alcohols

    OpenAIRE

    Li, Zhi; Zhang, Wei; Hisashi Yamamoto, H.

    2008-01-01

    Vanadium-catalyzed epoxidation has extended substrate scope. In addition to various bis-allylic alcohols, bis-homoallylic alcohols can also be desymmetrized using our Vanadium-Bis-hydroxamic acid complexes.

  10. Rhodium(III)- and iridium(III)-catalyzed C7 alkylation of indolines with diazo compounds.

    Science.gov (United States)

    Ai, Wen; Yang, Xueyan; Wu, Yunxiang; Wang, Xuan; Li, Yuanchao; Yang, Yaxi; Zhou, Bing

    2014-12-22

    A Rh(III)-catalyzed procedure for the C7-selective C-H alkylation of various indolines with α-diazo compounds at room temperature is reported. The advantages of this process are: 1) simple, mild, and pH-neutral reaction conditions, 2) broad substrate scope, 3) complete regioselectivity, 4) no need for an external oxidant, and 5) N2 as the sole byproduct. Furthermore, alkylation and bis-alkylation of carbazoles at the C1 and C8 positions have also been developed. More significantly, for the first time, a successful Ir(III)-catalyzed intermolecular insertion of arene C-H bonds into α-diazo compounds is reported. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Automated Quantum Mechanical Predictions of Enantioselectivity in a Rhodium-Catalyzed Asymmetric Hydrogenation.

    Science.gov (United States)

    Guan, Yanfei; Wheeler, Steven E

    2017-07-24

    A computational toolkit (AARON: An automated reaction optimizer for new catalysts) is described that automates the density functional theory (DFT) based screening of chiral ligands for transition-metal-catalyzed reactions with well-defined reaction mechanisms but multiple stereocontrolling transition states. This is demonstrated for the Rh-catalyzed asymmetric hydrogenation of (E)-β-aryl-N-acetyl enamides, for which a new C 2 -symmetric phosphorus ligand is designed. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Optimization of lipase-catalyzed enantioselective production of 1-phenyl 1-propanol using response surface methodology.

    Science.gov (United States)

    Soyer, Asli; Bayraktar, Emine; Mehmetoglu, Ulku

    2010-01-01

    Optically active 1-phenyl 1-propanol is used as a chiral building block and synthetic intermediate in the pharmaceutical industries. In this study, the enantioselective production of 1-phenyl 1-propanol was investigated systematically using response surface methodology (RSM). Before RSM was applied, the effects of the enzyme source, the type of acyl donor, and the type of solvent on the kinetic resolution of 1-phenyl 1-propanol were studied. The best results were obtained with Candida antartica lipase (commercially available as Novozym 435), vinyl laurate as the acyl donor, and isooctane as the solvent. In the RSM, substrate concentration, molar ratio of acyl donor to the substrate, amount of enzyme, temperature, and stirring rate were chosen as independent variables. The predicted optimum conditions for a higher enantiomeric excess (ee) were as follows: substrate concentration, 233 mM; molar ratio of acyl donor to substrate, 1.5; enzyme amount, 116 mg; temperature, 47 °C; and stirring rate, 161 rpm. A verification experiment conducted at these optimized conditions for maximum ee yielded 91% for 3 hr, which is higher than the predicted value of 83%. The effect of microwave on the ee was also investigated and ee reached 87% at only 5 min.

  13. Enantioselective conjugate addition of diethylzinc to chalcone catalyzed by Co(acac)(2) and chiral amino alcohols

    NARCIS (Netherlands)

    de Vries, A.H.M.; Feringa, B.L.

    1997-01-01

    Co(acac)(2) in the presence of chiral ligands has been employed as catalyst for the enantioselective conjugate addition of diethylzinc to chalcone. With chiral amino alcohols derived from (+)-camphor, enantioselectivities up to 83% were achieved. (C) 1997 Elsevier Science Ltd.

  14. Cu(I)-Catalyzed Enantioselective Friedel-Crafts Alkylation of Indoles with 2-Aryl-N-sulfonylaziridines as Alkylating Agents.

    Science.gov (United States)

    Ge, Chen; Liu, Ren-Rong; Gao, Jian-Rong; Jia, Yi-Xia

    2016-07-01

    A highly enantioselective Friedel-Crafts alkylation of indoles with N-sulfonylaziridines as alkylating agents has been developed by utilizing the complex of Cu(CH3CN)4BF4/(S)-Segphos as a catalyst. A range of optically active tryptamine derivatives are obtained in good to excellent yields and enantioselectivities (up to >99% ee) via a kinetic resolution process.

  15. A chiral Brønsted acid-catalyzed highly enantioselective Mannich-type reaction of α-diazo esters with in situ generated N-acyl ketimines.

    Science.gov (United States)

    Unhale, Rajshekhar A; Sadhu, Milon M; Ray, Sumit K; Biswas, Rayhan G; Singh, Vinod K

    2018-04-03

    A chiral phosphoric acid-catalyzed asymmetric Mannich-type reaction of α-diazo esters with in situ generated N-acyl ketimines, derived from 3-hydroxyisoindolinones has been demonstrated in this communication. A variety of isoindolinone-based α-amino diazo esters bearing a quaternary stereogenic center were afforded in high yields (up to 99%) with excellent enantioselectivities (up to 99% ee). Furthermore, the synthetic utility of the products has been depicted by the hydrogenation of the diazo moiety of adducts.

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

    Directory of Open Access Journals (Sweden)

    Kankan Zhang

    2013-05-01

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

  17. Enantioselective Alkylation of 2-Oxindoles Catalyzed by a Bifunctional Phase-Transfer Catalyst: Synthesis of (-)-Debromoflustramine B.

    Science.gov (United States)

    Craig, Ryan; Sorrentino, Emiliano; Connon, Stephen J

    2018-03-26

    A new bifunctional phase-transfer catalyst that employs hydrogen bonding as a control element was developed to promote efficient enantioselective S N 2 reactions for the construction all-carbon quaternary stereocenters in high yield and excellent enantioselectivity (up to 97 % ee) utilizing the alkylation of a malleable oxindole substrate. The utility of the methodology was demonstrated through a concise and highly enantioselective synthesis of (-)-debromoflustramine B. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. CO2 as a C1-organic building block: Enantioselective electrocarboxylation of aromatic ketones with CO2catalyzed by cinchona alkaloids under mild conditions

    International Nuclear Information System (INIS)

    Chen, Bao-Li; Tu, Zhuo-Ying; Zhu, Hong-Wei; Sun, Wen-Wen; Wang, Huan; Lu, Jia-Xing

    2014-01-01

    Highlights: •Cinchona alkaloids catalysis achieve enantioselective electrocarboxylation of racemic aromatic ketones. •The applications of CO 2 enantioselective electrochemical fixation into optically active hydroxyl carboxylic acids have been expanded. •The applications of alkaloids have been expanded. •The applications of asymmetric synthesis by electrochemical methodology have been expanded. -- Abstract: The enantioselective electrocarboxylation of pro-chiral aromatic ketones (2-acetonaphthone, 1-(6-methoxy-2-naphthyl)ethanone, 1-(4-methoxy-1-naphthyl)ethanone) with atmospheric pressure of CO 2 catalyzed by cinchona alkaloids in the presence of phenol was investigated in an undivided cell for the first time to give optically active 2-hydroxy-2-arylpropionic acid. For the model compound 2-acetonaphthone, the influence of various reaction conditions, such as cathode material, current density, catalyst type, ratio of proton to catalyst and catalyst quantity, on the enantiomeric excesses (ee) and yield has been investigated. Under the optimized conditions of 2-acetonaphthone, all the aromatic ketones examined are converted into corresponding optically active 2-hydroxy-2-arylpropionic acids in moderate yield (32.2% - 41.3%) and ee (48.1% - 48.6%). In addition, the electrochemical behavior of 2-acetonaphthone has been studied by cyclic voltammetry (CV) in the absence and presence of CO 2 . Moreover, the probable reaction pathway was proposed accordingly

  19. Norcoclaurine Synthase: Mechanism of an Enantioselective Pictet-Spengler Catalyzing Enzyme

    Directory of Open Access Journals (Sweden)

    Alberto Macone

    2010-03-01

    Full Text Available The use of bifunctional catalysts in organic synthesis finds inspiration in the selectivity of enzymatic catalysis which arises from the specific interactions between basic and acidic amino acid residues and the substrate itself in order to stabilize developing charges in the transition state. Many enzymes act as bifunctional catalysts using amino acid residues at the active site as Lewis acids and Lewis bases to modify the substrate as required for the given transformation. They bear a clear advantage over non-biological methods for their ability to tackle problems related to the synthesis of enantiopure compounds as chiral building blocks for drugs and agrochemicals. Moreover, enzymatic synthesis may offer the advantage of a clean and green synthetic process in the absence of organic solvents and metal catalysts. In this work the reaction mechanism of norcoclaurine synthase is described. This enzyme catalyzes the Pictet-Spengler condensation of dopamine with 4-hydroxyphenylacetaldehyde (4-HPAA to yield the benzylisoquinoline alkaloids central precursor, (S-norcoclaurine. Kinetic and crystallographic data suggest that the reaction mechanism occurs according to a typical bifunctional catalytic process.

  20. Enantioselective resolution of (R,S)-1-phenylethanol catalyzed by lipases immobilized in starch films

    International Nuclear Information System (INIS)

    Hoffmann, Isabel; Silva, Vanessa D.; Nascimento, Maria da G.

    2011-01-01

    Lipases from different sources and two mycelium-bound lipases, in a free or immobilized form, in ginger starch film were screened as biocatalysts in the reaction of (R,S)-1-phenylethanol (1) with vinyl acetate and other acylating agents. The effect of various reaction parameters in the resolution of (1) catalyzed by lipase from Burkholderia cepacia (BCL) immobilized in ginger starch film was evaluated (acyl donor type, alcohol:acyl donor molar ratio, temperature and organic solvent). The catalytic efficiency of BCL immobilized in polymeric blends of ginger starch and polyethylene oxide (PEO), in different compositions, was also studied. Vinyl acetate and iso-propenyl acetate furnished the highest conversion (9%) and enantiomeric excess (> 99%) of the (R)-ester. The alcohol:acyl donor molar ratio and temperature optimum were 1:1 and 28 deg respectively. The mixture of n-hexane/glycerol (9:1 v:v) was the most adequate for this reaction (conversion 23%, E > 200). The ginger starch/PEO (7:3 m/m) blend was successfully reused six times consecutively. (author)

  1. Enantioselective resolution of (R,S)-1-phenylethanol catalyzed by lipases immobilized in starch films

    Energy Technology Data Exchange (ETDEWEB)

    Hoffmann, Isabel; Silva, Vanessa D.; Nascimento, Maria da G., E-mail: graca@qmc.ufsc.b [Universidade Federal de Santa Catarina (UFSC), Florianopolis, SC (Brazil). Dept. de Quimica

    2011-07-01

    Lipases from different sources and two mycelium-bound lipases, in a free or immobilized form, in ginger starch film were screened as biocatalysts in the reaction of (R,S)-1-phenylethanol (1) with vinyl acetate and other acylating agents. The effect of various reaction parameters in the resolution of (1) catalyzed by lipase from Burkholderia cepacia (BCL) immobilized in ginger starch film was evaluated (acyl donor type, alcohol:acyl donor molar ratio, temperature and organic solvent). The catalytic efficiency of BCL immobilized in polymeric blends of ginger starch and polyethylene oxide (PEO), in different compositions, was also studied. Vinyl acetate and iso-propenyl acetate furnished the highest conversion (9%) and enantiomeric excess (> 99%) of the (R)-ester. The alcohol:acyl donor molar ratio and temperature optimum were 1:1 and 28 deg respectively. The mixture of n-hexane/glycerol (9:1 v:v) was the most adequate for this reaction (conversion 23%, E > 200). The ginger starch/PEO (7:3 m/m) blend was successfully reused six times consecutively. (author)

  2. Ruthenium Catalyzed Diastereo- and Enantioselective Coupling of Propargyl Ethers with Alcohols: Siloxy-Crotylation via Hydride Shift Enabled Conversion of Alkynes to π-Allyls.

    Science.gov (United States)

    Liang, Tao; Zhang, Wandi; Chen, Te-Yu; Nguyen, Khoa D; Krische, Michael J

    2015-10-14

    The first enantioselective carbonyl crotylations through direct use of alkynes as chiral allylmetal equivalents are described. Chiral ruthenium(II) complexes modified by Josiphos (SL-J009-1) catalyze the C-C coupling of TIPS-protected propargyl ether 1a with primary alcohols 2a-2o to form products of carbonyl siloxy-crotylation 3a-3o, which upon silyl deprotection-reduction deliver 1,4-diols 5a-5o with excellent control of regio-, anti-diastereo-, and enantioselectivity. Structurally related propargyl ethers 1b and 1c bearing ethyl- and phenyl-substituents engage in diastereo- and enantioselective coupling, as illustrated in the formation of adducts 5p and 5q, respectively. Selective mono-tosylation of diols 5a, 5c, 5e, 5f, 5k, and 5m is accompanied by spontaneous cyclization to deliver the trans-2,3-disubstituted furans 6a, 6c, 6e, 6f, 6k, and 6m, respectively. Primary alcohols 2a, 2l, and 2p were converted to the siloxy-crotylation products 3a, 3l, and 3p, which upon silyl deprotection-lactol oxidation were transformed to the trans-4,5-disubstituted γ-butyrolactones 7a, 7l, and 7p. The formation of 7p represents a total synthesis of (+)-trans-whisky lactone. Unlike closely related ruthenium catalyzed alkyne-alcohol C-C couplings, deuterium labeling studies provide clear evidence of a novel 1,2-hydride shift mechanism that converts metal-bound alkynes to π-allyls in the absence of intervening allenes.

  3. 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

  4. 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.

  5. A Readily Accessible Class of Chiral Cp Ligands and their Application in RuII -Catalyzed Enantioselective Syntheses of Dihydrobenzoindoles.

    Science.gov (United States)

    Wang, Shou-Guo; Park, Sung Hwan; Cramer, Nicolai

    2018-05-04

    Chiral cyclopentadienyl (Cp x ) ligands have a large application potential in enantioselective transition-metal catalysis. However, the development of concise and practical routes to such ligands remains in its infancy. We present a convenient and efficient two-step synthesis of a novel class of chiral Cp x ligands with tunable steric properties that can be readily used for complexation, giving Cp x Rh I , Cp x Ir I , and Cp x Ru II complexes. The potential of this ligand class is demonstrated with the latter in the enantioselective cyclization of azabenzonorbornadienes with alkynes, affording dihydrobenzoindoles in up to 98:2 e.r., significantly outperforming existing binaphthyl-derived Cp x ligands. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. 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....

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

    KAUST Repository

    Yang, Limin; Wang, Fei; Lee, Richmond; Lv, Yunbo; Huang, Kuo-Wei; Zhong, Guofu

    2014-01-01

    A facile N-heterocyclic carbene catalytic enantioselective aza-Diels-Alder reaction of oxodiazenes with α-chloroaldehydes as dienophile precursors is reported, with excellent enantioselectivity (ee > 99%) and excellent yield (up to 93%). DFT study

  8. The origin of enantioselectivity in the l-threonine-derived phosphine-sulfonamide catalyzed aza-Morita-Baylis-Hillman reaction: Effects of the intramolecular hydrogen bonding

    KAUST Repository

    Lee, Richmond

    2013-01-01

    l-Threonine-derived phosphine-sulfonamide 4 was identified as the most efficient catalyst to promote enantioselective aza-Morita-Baylis-Hillman (MBH) reactions, affording the desired aza-MBH adducts with excellent enantioselectivities. Density functional theory (DFT) studies were carried out to elucidate the origin of the observed enantioselectivity. The importance of the intramolecular N-H⋯O hydrogen-bonding interaction between the sulfonamide and enolate groups was identified to be crucial in inducing a high degree of stereochemical control in both the enolate addition to imine and the subsequent proton transfer step, affording aza-MBH reactions with excellent enantioselectivity. © 2013 The Royal Society of Chemistry.

  9. High enantioselective Novozym 435-catalyzed esterification of (R,S)-flurbiprofen monitored with a chiral stationary phase.

    Science.gov (United States)

    Siódmiak, Tomasz; Mangelings, Debby; Vander Heyden, Yvan; Ziegler-Borowska, Marta; Marszałł, Michał Piotr

    2015-03-01

    Lipases form Candida rugosa and Candida antarctica were tested for their application in the enzymatic kinetic resolution of (R,S)-flurbiprofen by enantioselective esterification. Successful chromatographic separation with well-resolved peaks of (R)- and (S)-flurbiprofen and their esters was achieved in one run on chiral stationary phases by high-performance liquid chromatography (HPLC). In this study screening of enzymes was performed, and Novozym 435 was selected as an optimal catalyst for obtaining products with high enantiopurity. Additionally, the influence of organic solvents (dichloromethane, dichloroethane, dichloropropane, and methyl tert-butyl ether), primary alcohols (methanol, ethanol, n-propanol, and n-butanol), reaction time, and temperature on the enantiomeric ratio and conversion was tested. The high values of enantiomeric ratio (E in the range of 51.3-90.5) of the esterification of (R,S)-flurbiprofen were obtained for all tested alcohols using Novozym 435, which have a great significance in the field of biotechnological synthesis of drugs. The optimal temperature range for the performed reactions was from 37 to 45 °C. As a result of the optimization, (R)-flurbiprofen methyl ester was obtained with a high optical purity, eep = 96.3 %, after 96 h of incubation. The enantiomeric ratio of the reaction was E = 90.5 and conversion was C = 35.7 %.

  10. Z-Selective iridium-catalyzed cross-coupling of allylic carbonates and α-diazo esters.

    Science.gov (United States)

    Thomas, Bryce N; Moon, Patrick J; Yin, Shengkang; Brown, Alex; Lundgren, Rylan J

    2018-01-07

    A well-defined Ir-allyl complex catalyzes the Z -selective cross-coupling of allyl carbonates with α-aryl diazo esters. The process overrides the large thermodynamic preference for E -products typically observed in metal-mediated coupling reactions to enable the synthesis of Z , E -dieneoates in good yield with selectivities consistently approaching or greater than 90 : 10. This transformation represents the first productive merger of Ir-carbene and Ir-allyl species, which are commonly encountered intermediates in allylation and cyclopropanation/E-H insertion catalysis. Potentially reactive functional groups (aryl halides, ketones, nitriles, olefins, amines) are tolerated owing to the mildness of reaction conditions. Kinetic analysis of the reaction suggests oxidative addition of the allyl carbonate to an Ir-species is rate-determining. Mechanistic studies uncovered a pathway for catalyst activation mediated by NEt 3 .

  11. Highly Enantioselective Construction of Tertiary Thioethers and Alcohols via Phosphine-Catalyzed Asymmetric γ-Addition reactions of 5H-Thiazol-4-ones and 5H-Oxazol-4-ones: Scope and Mechanistic Understandings

    KAUST Repository

    Wang, Tianli

    2015-06-02

    Phosphine-catalyzed highly enantioselective γ-additions of 5H-thiazol-4-ones and 5H-oxazol-4-ones to allenoates have been developed for the first time. With the employment of amino-acid derived bifunctional phosphines, a wide range of substituted 5H-thiazol-4-one and 5H-oxazol-4-one derivatives bearing heteroarom (S or O)-containing tertiary chiral centers were constructed in high yields and excellent enantioselectivities. The reported method provides a facile access to enantioenriched tertiary thioether/alcohols. The mechanism of γ-addition reaction was investigated by performing DFT calculations, and the hydrogen bonding interactions between the Brønsted acid moiety of the phosphine catalysts and the “C=O” unit of donor molecules were shown to be crucial in asymmetric induction.

  12. Highly Enantioselective Construction of Tertiary Thioethers and Alcohols via Phosphine-Catalyzed Asymmetric γ-Addition reactions of 5H-Thiazol-4-ones and 5H-Oxazol-4-ones: Scope and Mechanistic Understandings

    KAUST Repository

    Wang, Tianli; Yu, Zhaoyuan; Hoon, Ding Long; Huang, Kuo-Wei; Lan, Yu; Lu, Yixin

    2015-01-01

    Phosphine-catalyzed highly enantioselective γ-additions of 5H-thiazol-4-ones and 5H-oxazol-4-ones to allenoates have been developed for the first time. With the employment of amino-acid derived bifunctional phosphines, a wide range of substituted 5H-thiazol-4-one and 5H-oxazol-4-one derivatives bearing heteroarom (S or O)-containing tertiary chiral centers were constructed in high yields and excellent enantioselectivities. The reported method provides a facile access to enantioenriched tertiary thioether/alcohols. The mechanism of γ-addition reaction was investigated by performing DFT calculations, and the hydrogen bonding interactions between the Brønsted acid moiety of the phosphine catalysts and the “C=O” unit of donor molecules were shown to be crucial in asymmetric induction.

  13. The enantioselective total synthesis of (+)-clusianone.

    Science.gov (United States)

    Horeischi, Fiene; Guttroff, Claudia; Plietker, Bernd

    2015-02-11

    (+)-Clusianone, an exo-type B PPAP with reported anti-HIV and chemoprotective activities, was synthesized in eleven steps with 97% ee starting from acetylacetone. An enantioselective decarboxylative Tsuji-Trost-allylation and a Ru-catalyzed ring-closing metathesis-decarboxylative allylation were used to control both diastereo- and enantioselectivity.

  14. 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.

  15. Regio- and enantioselective synthesis of N-substituted pyrazoles by rhodium-catalyzed asymmetric addition to allenes.

    Science.gov (United States)

    Haydl, Alexander M; Xu, Kun; Breit, Bernhard

    2015-06-08

    The rhodium-catalyzed asymmetric N-selective coupling of pyrazole derivatives with terminal allenes gives access to enantioenriched secondary and tertiary allylic pyrazoles, which can be employed for the synthesis of medicinally important targets. The reaction tolerates a large variety of functional groups and labelling experiments gave insights into the reaction mechanism. This new methodology was further applied in a highly efficient synthesis of JAK 1/2 inhibitor (R)-ruxolitinib. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. 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.

  17. The origin of enantioselectivity in the l-threonine-derived phosphine-sulfonamide catalyzed aza-Morita-Baylis-Hillman reaction: Effects of the intramolecular hydrogen bonding

    KAUST Repository

    Lee, Richmond; Zhong, Fangrui; Zheng, Bin; Meng, Yuezhong; Lu, Yixin; Huang, Kuo-Wei

    2013-01-01

    in inducing a high degree of stereochemical control in both the enolate addition to imine and the subsequent proton transfer step, affording aza-MBH reactions with excellent enantioselectivity. © 2013 The Royal Society of Chemistry.

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

    KAUST Repository

    Yang, Limin

    2014-08-01

    A facile N-heterocyclic carbene catalytic enantioselective aza-Diels-Alder reaction of oxodiazenes with α-chloroaldehydes as dienophile precursors is reported, with excellent enantioselectivity (ee > 99%) and excellent yield (up to 93%). DFT study showed that cis-TSa, formed from a top face approach of oxodiazene to cis-IIa, is the most favorable transition state and is consistent with the experimental observations. © 2014 American Chemical Society.

  19. Rhodium-Catalyzed Asymmetric N-H Functionalization of Quinazolinones with Allenes and Allylic Carbonates: The First Enantioselective Formal Total Synthesis of (-)-Chaetominine.

    Science.gov (United States)

    Zhou, Yirong; Breit, Bernhard

    2017-12-22

    An unprecedented asymmetric N-H functionalization of quinazolinones with allenes and allylic carbonates was successfully achieved by rhodium catalysis with the assistance of chiral bidentate diphosphine ligands. The high efficiency and practicality of this method was demonstrated by a low catalyst loading of 1 mol % as well as excellent chemo-, regio-, and enantioselectivities with broad functional group compatibility. Furthermore, this newly developed strategy was applied as key step in the first enantioselective formal total synthesis of (-)-chaetominine. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Rhodium/chiral diene-catalyzed asymmetric 1,4-addition of arylboronic acids to chromones: a highly enantioselective pathway for accessing chiral flavanones.

    Science.gov (United States)

    He, Qijie; So, Chau Ming; Bian, Zhaoxiang; Hayashi, Tamio; Wang, Jun

    2015-03-01

    Chromone has been noted to be one of the most challenging substrates in the asymmetric 1,4-addition of α,β-unsaturated carbonyl compounds. By employing the rhodium complex associated with a chiral diene ligand, (R,R)-Ph-bod*, the 1,4-addition of a variety of arylboronic acids was realized to give high yields of the corresponding flavanones with excellent enantioselectivities (≥97% ee, 99% ee for most substrates). Ring-opening side products, which would lead to erosion of product enantioselectivity, were not observed under the stated reaction conditions. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Reversible Interconversion between 2,5-Dimethylpyrazine and 2,5-Dimethylpiperazine by Iridium-Catalyzed Hydrogenation/Dehydrogenation for Efficient Hydrogen Storage.

    Science.gov (United States)

    Fujita, Ken-Ichi; Wada, Tomokatsu; Shiraishi, Takumi

    2017-08-28

    A new hydrogen storage system based on the hydrogenation and dehydrogenation of nitrogen heterocyclic compounds, employing a single iridium catalyst, has been developed. Efficient hydrogen storage using relatively small amounts of solvent compared with previous systems was achieved by this new system. Reversible transformations between 2,5-dimethylpyrazine and 2,5-dimethylpiperazine, accompanied by the uptake and release of three equivalents of hydrogen, could be repeated almost quantitatively at least four times without any loss of efficiency. Furthermore, hydrogen storage under solvent-free conditions was also accomplished. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Kinetic mechanism and enantioselectivity of halohydrin dehalogenase from Agrobacterium radiobacter

    NARCIS (Netherlands)

    Tang, Lixia; Lutje Spelberg, Jeffrey H.; Fraaije, Marco W.; Janssen, DB

    2003-01-01

    Halohydrin dehalogenase (HheC) from Agrobacterium radiobacter AD1 catalyzes the reversible intramolecular nucleophilic displacement of a halogen by a hydroxyl group in vicinal haloalcohols, producing the corresponding epoxides. The enzyme displays high enantioselectivity toward some aromatic

  3. The Brønsted Acid-Catalyzed, Enantioselective Aza-Diels-Alder Reaction for the Direct Synthesis of Chiral Piperidones.

    Science.gov (United States)

    Weilbeer, Claudia; Sickert, Marcel; Naumov, Sergei; Schneider, Christoph

    2017-01-12

    We disclose herein the first enantioselective aza-Diels-Alder reaction of β-alkyl-substituted vinylketene silyl-O,O-acetals and imines furnishing a broad range of optically highly enriched 4-alkyl-substituted 2-piperidones. As a catalyst for this one-pot reaction we employed a chiral phosphoric acid which effects a vinylogous Mannich reaction directly followed by ring-closure to the lactam. Subsequent fully diastereoselective transformations including hydrogenation, enolate alkylation, and lactam alkylation/reduction processes converted the cycloadducts into various highly substituted piperidines of great utility for the synthesis of natural products and medicinally active compounds. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Enantioselective ProPhenol-catalyzed addition of 1,3-diynes to aldehydes to generate synthetically versatile building blocks and diyne natural products.

    Science.gov (United States)

    Trost, Barry M; Chan, Vincent S; Yamamoto, Daisuke

    2010-04-14

    A highly enantioselective method for the catalytic addition of terminal 1,3-diynes to aldehydes was developed using our dinuclear zinc ProPhenol (1) system. Furthermore, triphenylphosphine oxide was found to interact synergistically with the catalyst to substantially enhance the chiral recognition. The generality of this catalytic transformation was demonstrated with aryl, alpha,beta-unsaturated and saturated aldehydes, of which the latter were previously limited in alkynyl zinc additions. The chiral diynol products are also versatile building blocks that can be readily elaborated; this was illustrated through highly selective trans-hydrosilylations, which enabled the synthesis of a beta-hydroxyketone and enyne. Additionally, the development of this method allowed for the rapid total syntheses of several biologically important diynol-containing natural products.

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

    NARCIS (Netherlands)

    Knol, Joop; Meetsma, Auke; Feringa, Bernard

    1995-01-01

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

  6. (+)-camphor-derived tri- and tetradentate amino alcohols; synthesis and application as ligands in the nickel catalyzed enantioselective conjugate addition of diethylzinc

    NARCIS (Netherlands)

    Vries, André H.M. de; Imbos, Rosalinde; Feringa, Bernard

    1997-01-01

    Several novel tri- and tetradentate amino alcohol ligands, all derived from (+)-camphor, have been synthesized by using specific N-alkylation procedures. The amino alcohols were employed as chiral ligands in the nickel catalyzed conjugate additions of diethylzine to chalcone and cyclohexenone as

  7. Synthesis of Donor/Acceptor-Substituted Diazo Compounds in Flow and Their Application in Enantioselective Dirhodium-Catalyzed Cyclopropanation and C-H Functionalization.

    Science.gov (United States)

    Rackl, Daniel; Yoo, Chun-Jae; Jones, Christopher W; Davies, Huw M L

    2017-06-16

    A tandem reaction system has been developed for the preparation of donor/acceptor-substituted diazo compounds in continuous flow coupled to dirhodium-catalyzed C-H functionalization or cyclopropanation. Hydrazones were oxidized in flow by solid-supported N-iodo-p-toluenesulfonamide potassium salt (PS-SO 2 NIK) to generate the diazo compounds, which were then purified by passing through a column of molecular sieves/sodium thiosulfate.

  8. Enantioselective rhodium enolate protonations. A new methodology for the synthesis of beta2-amino acids.

    Science.gov (United States)

    Sibi, Mukund P; Tatamidani, Hiroto; Patil, Kalyani

    2005-06-23

    [reaction: see text] Rhodium-catalyzed conjugate addition of an aryl boronic acid to alpha-methylamino acrylates followed by enantioselective protonation of the oxa-pi-allylrhodium intermediate provides access to aryl-substituted beta(2)-amino acids. The impact of the different variables of the reaction on the levels of enantioselectivity has been assessed.

  9. Enantioselective Rhodium Enolate Protonations. A New Methodology for the Synthesis of β2-Amino Acids

    Science.gov (United States)

    Sibi, Mukund P.; Tatamidani, Hiroto; Patil, Kalyani

    2008-01-01

    Rhodium catalyzed conjugate addition of an aryl boronic acid to α-methylamino acrylates followed by enantioselective protonation of the oxa-π-allylrhodium intermediate provides access to aryl substituted β2-amino acids. The impact of the different variables of the reaction on the levels of enantioselectivity has been assessed. PMID:15957893

  10. DNA-based catalytic enantioselective intermolecular oxa-Michael addition reactions

    NARCIS (Netherlands)

    Megens, Rik P.; Roelfes, Gerard

    2012-01-01

    Using the DNA-based catalysis concept, a novel Cu(II) catalyzed enantioselective oxa-Michael addition of alcohols to enones is reported. Enantioselectivities of up to 86% were obtained. The presence of water is important for the reactivity, possibly by reverting unwanted side reactions such as

  11. Enantioselective Rhodium-Catalyzed [2+2+2] Cycloadditions of Terminal Alkynes and Alkenyl Isocyanates: Mechanistic Insights Lead to a Unified Model that Rationalizes Product Selectivity

    Science.gov (United States)

    Dalton, Derek M.; Oberg, Kevin M.; Yu, Robert T.; Lee, Ernest E.; Perreault, Stéphane; Oinen, Mark Emil; Pease, Melissa L.; Malik, Guillaume; Rovis, Tomislav

    2009-01-01

    This manuscript describes the development and scope of the asymmetric rhodium-catalyzed [2+2+2] cycloaddition of terminal alkynes and alkenyl isocyanates leading to the formation of indolizidine and quinolizidine scaffolds. The use of phosphoramidite ligands proved crucial for avoiding competitive terminal alkyne dimerization. Both aliphatic and aromatic terminal alkynes participate well, with product selectivity a function of both the steric and electronic character of the alkyne. Manipulation of the phosphoramidite ligand leads to tuning of enantio- and product selectivity, with a complete turnover in product selectivity seen with aliphatic alkynes when moving from Taddol-based to biphenol-based phosphoramidites. Terminal and 1,1-disubstituted olefins are tolerated with nearly equal efficacy. Examination of a series of competition experiments in combination with analysis of reaction outcome shed considerable light on the operative catalytic cycle. Through a detailed study of a series of X-ray structures of rhodium(cod)chloride/phosphoramidite complexes, we have formulated a mechanistic hypothesis that rationalizes the observed product selectivity. PMID:19817441

  12. Infrared-thermographic screening of the activity and enantioselectivity of enzymes.

    Science.gov (United States)

    Reetz, M T; Hermes, M; Becker, M H

    2001-05-01

    The infrared radiation caused by the heat of reaction of an enantioselective enzyme-catalyzed transformation can be detected by modern photovoltaic infrared (IR)-thermographic cameras equipped with focal-plane array detectors. Specifically, in the lipase-catalyzed enantioselective acylation of racemic 1-phenylethanol, the (R)- and (S)-substrates are allowed to react separately in the wells of microtiter plates, the (R)-alcohol showing hot spots in the IR-thermographic images. Thus, highly enantioselective enzymes can be identified at kinetic resolution.

  13. Iridium Interfacial Stack (IRIS)

    Science.gov (United States)

    Spry, David James (Inventor)

    2015-01-01

    An iridium interfacial stack ("IrIS") and a method for producing the same are provided. The IrIS may include ordered layers of TaSi.sub.2, platinum, iridium, and platinum, and may be placed on top of a titanium layer and a silicon carbide layer. The IrIS may prevent, reduce, or mitigate against diffusion of elements such as oxygen, platinum, and gold through at least some of its layers.

  14. Enantioselective cycloadditions with alpha,beta-disubstituted acrylimides.

    Science.gov (United States)

    Sibi, Mukund P; Ma, Zhihua; Itoh, Kennosuke; Prabagaran, Narayanasamy; Jasperse, Craig P

    2005-06-09

    [reaction: see text] The use of N-H imide templates provides a solution to the problem of rotamer control in Lewis acid catalyzed reactions of alpha,beta-disubstituted acryloyl imides. Reactions proceed through the s-cis rotamer and with improved reactivity because A(1,3) strain is avoided. Enantioselective nitrone, nitrile oxide, and Diels-Alder cycloadditions demonstrate the principle.

  15. Iridium complexes for electrocatalysis

    Science.gov (United States)

    Sheehan, Stafford Wheeler; Hintermair, Ulrich; Thomsen, Julianne M; Brudvig, Gary W; Crabtree, Robert H

    2017-10-17

    Solution-phase (e.g., homogeneous) or surface-immobilized (e.g., heterogeneous) electrode-driven oxidation catalysts based on iridium coordination compounds which self-assemble upon chemical or electrochemical oxidation of suitable precursors and methods of making and using thereof are. Iridium species such as {[Ir(LX).sub.x(H.sub.2O).sub.y(.mu.-O)].sub.z.sup.m+}.sub.n wherein x, y, m are integers from 0-4, z and n from 1-4 and LX is an oxidation-resistant chelate ligand or ligands, such as such as 2(2-pyridyl)-2-propanolate, form upon oxidation of various molecular iridium complexes, for instance [Cp*Ir(LX)OH] or [(cod)Ir(LX)] (Cp*=pentamethylcyclopentadienyl, cod=cis-cis,1,5-cyclooctadiene) when exposed to oxidative conditions, such as sodium periodate (NaIO.sub.4) in aqueous solution at ambient conditions.

  16. Iridium: failures & successes

    Science.gov (United States)

    Christensen, CarissaBryce; Beard, Suzette

    2001-03-01

    This paper will provide an overview of the Iridium business venture in terms of the challenges faced, the successes achieved, and the causes of the ultimate failure of the venture — bankruptcy and system de-orbit. The paper will address technical, business, and policy issues. The intent of the paper is to provide a balanced and accurate overview of the Iridium experience, to aid future decision-making by policy makers, the business community, and technical experts. Key topics will include the history of the program, the objectives and decision-making of Motorola, the market research and analysis conducted, partnering strategies and their impact, consumer equipment availability, and technical issues — target performance, performance achieved, technical accomplishments, and expected and unexpected technical challenges. The paper will use as sources trade media and business articles on the Iridium program, technical papers and conference presentations, Wall Street analyst's reports, and, where possible, interviews with participants and close observers.

  17. Determination of the human cytochrome P450 monooxygenase catalyzing the enantioselective oxidation of 2,2',3,5',6-pentachlorobiphenyl (PCB 95) and 2,2',3,4,4',5',6-heptachlorobiphenyl (PCB 183).

    Science.gov (United States)

    Nagayoshi, Haruna; Kakimoto, Kensaku; Konishi, Yoshimasa; Kajimura, Keiji; Nakano, Takeshi

    2017-10-17

    2,2',3,5',6-Pentachlorobiphenyl (PCB 95) and 2,2',3,4,4',5',6-heptachlorobiphenyl (PCB 183) possess axial chirality and form the aS and aR enantiomers. The enantiomers of these congeners have been reported to accumulate in the human body enantioselectively via unknown mechanisms. In this study, we determined the cytochrome P450 (CYP) monooxygenase responsible for the enantioselective oxidization of PCB 95 and PCB 183, using a recombinant human CYP monooxygenase. We evaluated 13 CYP monooxygenases, namely CYP1A1, CYP1A2, CYP1B1, CYP2A6, CYP2B6, CYP2C8, CYP2C19, CYP2E1, CYP2J2, CYP3A4, CYP3A5, CYP4F2, and aromatase (CYP19), and revealed that CYP2A6 preferably oxidizes aS-PCB 95 enantioselectively; however, it did not oxidize PCB 183. The enantiomer composition was elevated from 0.5 (racemate) to 0.54. In addition, following incubation with CYP2A6, the enantiomer fraction (EF) of PCB 95 demonstrated a time-dependent increase.

  18. Molecular Design of a Chiral Brønsted Acid with Two Different Acidic Sites: Regio-, Diastereo-, and Enantioselective Hetero-Diels-Alder Reaction of Azopyridinecarboxylate with Amidodienes Catalyzed by Chiral Carboxylic Acid-Monophosphoric Acid.

    Science.gov (United States)

    Momiyama, Norie; Tabuse, Hideaki; Noda, Hirofumi; Yamanaka, Masahiro; Fujinami, Takeshi; Yamanishi, Katsunori; Izumiseki, Atsuto; Funayama, Kosuke; Egawa, Fuyuki; Okada, Shino; Adachi, Hiroaki; Terada, Masahiro

    2016-09-07

    A chiral Brønsted acid containing two different acidic sites, chiral carboxylic acid-monophosphoric acid 1a, was designed to be a new and effective concept in catalytic asymmetric hetero-Diels-Alder reactions of azopyridinecarboxylate with amidodienes. The multipoint hydrogen-bonding interactions among the carboxylic acid, monophosphoric acid, azopyridinecarboxylate, and amidodiene achieved high catalytic and chiral efficiency, producing substituted 1,2,3,6-tetrahydropyridazines with excellent stereocontrol in a single step. This constitutes the first example of regio-, diastereo-, and enantioselective azo-hetero-Diels-Alder reactions by chiral Brønsted acid catalysis.

  19. Enantioselective biotransformations of nitriles in organic synthesis.

    Science.gov (United States)

    Wang, Mei-Xiang

    2015-03-17

    The hydration and hydrolysis of nitriles are valuable synthetic methods used to prepare carboxamides and carboxylic acids. However, chemical hydration and hydrolysis of nitriles involve harsh reaction conditions, have low selectivity, and generate large amounts of waste. Therefore, researchers have confined the scope of these reactions to simple nitrile substrates. However, biological transformations of nitriles are highly efficient, chemoselective, and environmentally benign, which has led synthetic organic chemists and biotechologists to study these reactions in detail over the last two decades. In nature, biological systems degrade nitriles via two distinct pathways: nitrilases catalyze the direct hydrolysis of nitriles to afford carboxylic acids with release of ammonia, and nitrile hydratases catalyze the conversion of nitriles into carboxamides, which then furnish carboxylic acids via hydrolysis in the presence of amidases. Researchers have subsequently developed biocatalytic methods into useful industrial processes for the manufacture of commodity chemicals, including acrylamide. Since the late 1990s, research by my group and others has led to enormous progress in the understanding and application of enantioselective biotransformations of nitriles in organic synthesis. In this Account, I summarize the important advances in enantioselective biotransformations of nitriles and amides, with a primary focus on research from my laboratory. I describe microbial whole-cell-catalyzed kinetic resolution of various functionalized nitriles, amino- and hydroxynitriles, and nitriles that contain small rings and the desymmetrization of prochiral and meso dinitriles and diamides. I also demonstrate how we can apply the biocatalytic protocol to synthesize natural products and bioactive compounds. These nitrile biotransformations offer an attractive and unique protocol for the enantioselective synthesis of polyfunctionalized organic compounds that are not readily obtainable by

  20. cis-chlorobenzene dihydrodiol dehydrogenase (TcbB) from Pseudomonas sp. strain P51, expressed in Escherichia coli DH5alpha(pTCB149), catalyzes enantioselective dehydrogenase reactions.

    Science.gov (United States)

    Raschke, H; Fleischmann, T; Van Der Meer, J R; Kohler, H P

    1999-12-01

    cis-Chlorobenzene dihydrodiol dehydrogenase (CDD) from Pseudomonas sp. strain P51, cloned into Escherichia coli DH5alpha(pTCB149) was able to oxidize cis-dihydrodihydroxy derivatives (cis-dihydrodiols) of dihydronaphthalene, indene, and four para-substituted toluenes to the corresponding catechols. During the incubation of a nonracemic mixture of cis-1,2-indandiol, only the (+)-cis-(1R,2S) enantiomer was oxidized; the (-)-cis-(S,2R) enantiomer remained unchanged. CDD oxidized both enantiomers of cis-1,2-dihydroxy-1,2,3, 4-tetrahydronaphthalene, but oxidation of the (+)-cis-(1S,2R) enantiomer was delayed until the (-)-cis-(1R,2S) enantiomer was completely depleted. When incubated with nonracemic mixtures of para-substituted cis-toluene dihydrodiols, CDD always oxidized the major enantiomer at a higher rate than the minor enantiomer. When incubated with racemic 1-indanol, CDD enantioselectively transformed the (+)-(1S) enantiomer to 1-indanone. This stereoselective transformation shows that CDD also acted as an alcohol dehydrogenase. Additionally, CDD was able to oxidize (+)-cis-(1R,2S)-dihydroxy-1, 2-dihydronaphthalene, (+)-cis-monochlorobiphenyl dihydrodiols, and (+)-cis-toluene dihydrodiol to the corresponding catechols.

  1. cis-Chlorobenzene Dihydrodiol Dehydrogenase (TcbB) from Pseudomonas sp. Strain P51, Expressed in Escherichia coli DH5α(pTCB149), Catalyzes Enantioselective Dehydrogenase Reactions

    Science.gov (United States)

    Raschke, Henning; Fleischmann, Thomas; Van Der Meer, Jan Roelof; Kohler, Hans-Peter E.

    1999-01-01

    cis-Chlorobenzene dihydrodiol dehydrogenase (CDD) from Pseudomonas sp. strain P51, cloned into Escherichia coli DH5α(pTCB149) was able to oxidize cis-dihydrodihydroxy derivatives (cis-dihydrodiols) of dihydronaphthalene, indene, and four para-substituted toluenes to the corresponding catechols. During the incubation of a nonracemic mixture of cis-1,2-indandiol, only the (+)-cis-(1R,2S) enantiomer was oxidized; the (−)-cis-(S,2R) enantiomer remained unchanged. CDD oxidized both enantiomers of cis-1,2-dihydroxy-1,2,3,4-tetrahydronaphthalene, but oxidation of the (+)-cis-(1S,2R) enantiomer was delayed until the (−)-cis-(1R,2S) enantiomer was completely depleted. When incubated with nonracemic mixtures of para-substituted cis-toluene dihydrodiols, CDD always oxidized the major enantiomer at a higher rate than the minor enantiomer. When incubated with racemic 1-indanol, CDD enantioselectively transformed the (+)-(1S) enantiomer to 1-indanone. This stereoselective transformation shows that CDD also acted as an alcohol dehydrogenase. Additionally, CDD was able to oxidize (+)-cis-(1R,2S)-dihydroxy-1,2-dihydronaphthalene, (+)-cis-monochlorobiphenyl dihydrodiols, and (+)-cis-toluene dihydrodiol to the corresponding catechols. PMID:10583971

  2. Cis-Chlorobenzene dihydrodiol dehydrogenase (TcbB) from Pseudomonas sp. strain P51, expressed in Escherichia coli DH5{alpha}(pTCB149), catalyzes enantioselective dehydrogenase reactions

    Energy Technology Data Exchange (ETDEWEB)

    Raschke, H.; Fleischmann, T.; Meer, J.R. van der; Kohler, H.P.E.

    1999-12-01

    cis-Chlorobenzene dihydrodiol dehydrogenase (CDD) from Pseudomonas sp. strain P51, cloned into Escherichia coli DH5{alpha}(pTCB149) was able to oxidize cis-dihydrodihydroxy derivatives (cis-dihydrodiols) of dihydronaphthalene, indene, and four para-substituted toluenes to the corresponding catechols. During the incubation of a nonracemic mixture of cis-1,2-indandiol, only the (+)-cis-(1R,2S) enantiomer was oxidized; the (-)-cis-(S,2R) enantiomer remained unchanged, CDD oxidized both enantiomers of cis-1,2-dihydroxy-1,2,3,4-tetrahydronaphthalene, but oxidation of the (+)-cis-(1S,2R) enantiomer was delayed until the (-)-cis-(1R,2S) enantiomer was completely depleted. When incubated with nonracemic mixtures of para-substituted cis-toluene dihydrodiols, CDD always oxidized the major enantiomer at a higher rate than the minor enantiomer. When incubated with racemic 1-indanol, CDD enantioselectively transformed the (+)-(1S) enatiomer to 1-indanone. This stereoselective transformation shows that CDD also acted as an alcohol dehydrogenase. Additionally, CDD was able to oxidize (+)-cis-(1R,2S)-dihydroxy-1,2-dihydronaphthalene, (+)-cis-monochlorobiphenyl dihydrodiols, and (+)-cis-toluene dihydrodiol to the corresponding catechols.

  3. Catalytic Enantioselective Synthesis of 3,4-Unsubstituted Thiochromenes through Sulfa-Michael/Julia-Kocienski Olefination Cascade Reaction.

    Science.gov (United States)

    Simlandy, Amit Kumar; Mukherjee, Santanu

    2017-05-05

    A highly enantioselective cascade sulfa-Michael/Julia-Kocienski olefination reaction between 2-mercaptobenzaldehydes and β-substituted vinyl PT-sulfones has been realized for the synthesis of 3,4-unsubstituted 2H-thiochromenes. This reaction, catalyzed by diphenylprolinol TMS ether, proceeds through an aromatic iminium intermediate and furnishes a wide range of 2-substiuted 2H-thiochromenes with excellent enantioselectivities (up to 99:1 er).

  4. 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).

  5. Flexible Enantioselectivity of Tryptophanase Attributable to Benzene Ring in Heterocyclic Moiety of D-Tryptophan

    Directory of Open Access Journals (Sweden)

    Akihiko Shimada

    2012-05-01

    Full Text Available The invariance principle of enzyme enantioselectivity must be absolute because it is absolutely essential to the homochiral biological world. Most enzymes are strictly enantioselective, and tryptophanase is one of the enzymes with extreme absolute enantioselectivity for L-tryptophan. Contrary to conventional knowledge about the principle, tryptophanase becomes flexible to catalyze D-tryptophan in the presence of diammonium hydrogenphosphate. Since D-amino acids are ordinarily inert or function as inhibitors even though they are bound to the active site, the inhibition behavior of D-tryptophan and several inhibitors involved in this process was examined in terms of kinetics to explain the reason for this flexible enantioselectivity in the presence of diammonium hydrogenphosphate. Diammonium hydrogenphosphate gave tryptophanase a small conformational change so that D-tryptophan could work as a substrate. As opposed to other D-amino acids, D-tryptophan is a very bulky amino acid with a benzene ring in its heterocyclic moiety, and so we suggest that this structural feature makes the catalysis of D-tryptophan degradation possible, consequently leading to the flexible enantioselectivity. The present results not only help to understand the mechanism of enzyme enantioselectivity, but also shed light on the origin of homochirality.

  6. Asymmetric Chemoenzymatic Reductive Acylation of Ketones by a Combined Iron-Catalyzed Hydrogenation-Racemization and Enzymatic Resolution Cascade

    KAUST Repository

    El-Sepelgy, Osama; Brzozowska, Aleksandra; Rueping, Magnus

    2017-01-01

    . By merging the iron-catalyzed redox reactions with enantioselective enzymatic acylations a wide range of benzylic, aliphatic and (hetero)aromatic ketones, as well as diketones, were reductively acylated. The corresponding products were isolated with high

  7. Dual Enantioselective Control using D-phenylglycine-L-proline-derived Catalysts for the Enantioselective Addition of Diethylzinc to Aldehyde

    International Nuclear Information System (INIS)

    Kang, Seock Yong; Park, Yong Sun

    2016-01-01

    Dipeptide-derived catalysts are of great interest in various asymmetric transformations because of their short and simple preparation and easy modification of their modular structure by using different α-amino acids. We recently reported the first example of dipeptide-catalyzed enantioselective addition of dialkylzinc to aldehydes. We have developed a novel D-Phg-L-Pro dipeptide-derived catalyst for the addition of diethylzinc to aromatic aldehydes. We also disclosed an effective chiral switching by simply modifying nonchiral part of D-Phg-L-Pro dipeptide.

  8. Enantiomerization and enantioselective bioaccumulation of metalaxyl in Tenebrio molitor larvae.

    Science.gov (United States)

    Gao, Yongxin; Wang, Huili; Qin, Fang; Xu, Peng; Lv, Xiaotian; Li, Jianzhong; Guo, Baoyuan

    2014-02-01

    The enantiomerization and enantioselective bioaccumulation of metalaxyl by a single dose of exposure to Tenebrio molitor larvae under laboratory condition were studied by high-performance liquid chromatography tandem mass spectroscopy (HPLC-MS/MS) based on a ChiralcelOD-3R [cellulosetris-tris-(3, 5-dichlorophenyl-carbamate)] column. Exposure of enantiopure R-metalaxyl and S-metalaxyl in Tenebrio molitor larvae exhibited significant enantiomerization, with formation of the R enantiomers from the S enantiomers, and vice versa, which might be attributed to the chiral pesticide catalyzed by a certain enzyme in Tenebrio molitor larvae. Enantiomerization was not observed in wheat bran during the period of 21 d. In addition, bioaccumulation of rac-metalaxyl in Tenebrio molitor larvae was enantioselective with a preferential accumulation of S-metalaxyl. These results showed that enantioselectivity was caused not only by actual degradation and metabolism but also by enantiomerization, which was an important process in the environmental fate and behavior of metalaxyl enantiomers. Copyright © 2013 Wiley Periodicals, Inc.

  9. Highly selective cobalt-catalyzed hydrovinylation of styrene

    NARCIS (Netherlands)

    Grutters, M.M.P.; Müller, C.; Vogt, D.

    2006-01-01

    The hydrovinylation reaction is a codimerization of a 1,3-diene or vinyl arene and ethene with great potential for fine chemicals and pharmaceuticals. For the first time, enantioselective cobalt-catalyzed hydrovinylations of styrene were achieved with a cobalt-based system bearing a chiral

  10. Iridium-Catalyzed Regioselective Borylation of Substituted Biaryls

    KAUST Repository

    Chotana, Ghayoor

    2018-03-28

    Biarylboronic esters are generally prepared by directed ortho­ -metalation or by Miyaura borylation and hence rely on the presence of a directing group or pre-functionalization. In this paper, the preparation of biarylboronic esters by direct C–H borylation of biaryl substrates is reported. Sterically governed regioselectivities were observed in the borylation of appropriately substituted biaryls by using [Ir(OMe)(COD)] precatalyst and di- tert -butylbipyridyl ligand. The resulting biarylboronic esters were isolated in 38–98% yields. The synthesized biarylboronic esters were further successfully employed in C–O, C–Br, and C–C coupling reactions.

  11. Iridium-Catalyzed Regioselective Borylation of Substituted Biaryls

    KAUST Repository

    Chotana, Ghayoor; Asghar, Soneela; Shahzadi, Tayyaba; Alazmi, Meshari; Gao, Xin; Emwas, Abdul-Hamid M.; Saleem, Rahman; Batool, Farhat

    2018-01-01

    Biarylboronic esters are generally prepared by directed ortho­ -metalation or by Miyaura borylation and hence rely on the presence of a directing group or pre-functionalization. In this paper, the preparation of biarylboronic esters by direct C

  12. Exo selective enantioselective nitrone cycloadditions.

    Science.gov (United States)

    Sibi, Mukund P; Ma, Zhihua; Jasperse, Craig P

    2004-01-28

    We have developed a novel method for accessing exo adducts with high enantioselectivity in nitrone cycloadditions to enoates. Pyrazolidinones proved to be effective achiral templates in the cycloadditions, providing exo adducts typically in >15:1 selectivity and 90-98% ee. The use of Lewis acids that form square planar complexes, such as copper triflate, was important for obtaining high exo selectivity.

  13. Cyclopalladated complexes in enantioselective catalysis

    Energy Technology Data Exchange (ETDEWEB)

    Dunina, Valeria V; Gorunova, Olga N; Zykov, P A; Kochetkov, Konstantin A

    2011-01-31

    The results of the use of optically active palladacycles in enantioselective catalysis of [3,3]-sigmatropic rearrangements, aldol condensation, the Michael reaction and cross-coupling are analyzed. Reactions with allylic substrates or reagents and some other transformations are considered.

  14. Catalytic enantioselective Reformatsky reaction with ketones

    NARCIS (Netherlands)

    Fernandez-Ibanez, M. Angeles; Macia, Beatriz; Minnaard, Adriaan J.; Feringa, Ben L.

    2008-01-01

    Chiral tertiary alcohols were obtained with good yields and enantioselectivities via a catalytic Reformatsky reaction with ketones, including the challenging diaryl ketones, using chiral BINOL derivatives.

  15. Combining the catalytic enantioselective reaction of visible-light-generated radicals with a by-product utilization system.

    Science.gov (United States)

    Huang, Xiaoqiang; Luo, Shipeng; Burghaus, Olaf; Webster, Richard D; Harms, Klaus; Meggers, Eric

    2017-10-01

    We report an unusual reaction design in which a chiral bis-cyclometalated rhodium(iii) complex enables the stereocontrolled chemistry of photo-generated carbon-centered radicals and at the same time catalyzes an enantioselective sulfonyl radical addition to an alkene. Specifically, employing inexpensive and readily available Hantzsch esters as the photoredox mediator, Rh-coordinated prochiral radicals generated by a selective photoinduced single electron reduction are trapped by allyl sulfones in a highly stereocontrolled fashion, providing radical allylation products with up to 97% ee. The hereby formed fragmented sulfonyl radicals are utilized via an enantioselective radical addition to form chiral sulfones, which minimizes waste generation.

  16. An enantioselective approach toward 3,4-dihydroisocoumarin through the bromocyclization of styrene-type carboxylic acids.

    Science.gov (United States)

    Chen, Jie; Zhou, Ling; Tan, Chong Kiat; Yeung, Ying-Yeung

    2012-01-20

    A facile and enantioselective approach toward 3,4-dihydroisocoumarin was developed. The method involved an amino-thiocarbamate catalyzed enantioselective bromocyclization of styrene-type carboxylic acids, yielding 3-bromo-3,4-dihydroisocoumarins with good yields and ee's. 3-Bromo-3,4-dihydroisocoumarins are versatile building blocks for various dihydroisocoumarin derivatives in which the Br group can readily be modified to achieve biologically important 4-O-type and 4-N-type 3,4-dihydroisocoumarin systems. In addition, studies indicated that, by refining some parameters, the synthetically useful 5-exo phthalide products could be achieved with good yields and ee's.

  17. Construction of axial chirality by rhodium-catalyzed asymmetric dehydrogenative Heck coupling of biaryl compounds with alkenes.

    Science.gov (United States)

    Zheng, Jun; You, Shu-Li

    2014-11-24

    Enantioselective construction of axially chiral biaryls by direct C-H bond functionalization reactions has been realized. Novel axially chiral biaryls were synthesized by the direct C-H bond olefination of biaryl compounds, using a chiral [Cp*Rh(III)] catalyst, in good to excellent yields and enantioselectivities. The obtained axially chiral biaryls were found as suitable ligands for rhodium-catalyzed asymmetric conjugate additions. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Balancing activity, stability and conductivity of nanoporous core-shell iridium/iridium oxide oxygen evolution catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Yong-Tae; Lopes, Pietro Papa; Park, Shin-Ae; Lee, A-Yeong; Lim, Jinkyu; Lee, Hyunjoo; Back, Seoin; Jung, Yousung; Danilovic, Nemanja; Stamenkovic, Vojislav; Erlebacher, Jonah; Snyder, Joshua; Markovic, Nenad M.

    2017-11-13

    The selection of oxide materials for catalyzing the Oxygen Evolution Reaction in acid-based electrolyzers must be guided by the proper balance between activity, stability and conductivity – a challenging mission of great importance for delivering affordable and environmentally friendly hydrogen. Here we report that the highly conductive nanoporous architecture of an iridium oxide shell on a metallic iridium core, formed through the fast dealloying of osmium from an Ir25Os75 alloy, exhibits an exceptional balance between oxygen evolution activity and stability as quantified by the Activity-Stability FactorASF. Based on this metric, the nanoporous Ir/IrO2 morphology of dealloyed Ir25Os75 shows a factor of ~30 improvement ASFrelative to conventional Ir-based oxide materials and a ~8 times improvement over dealloyed Ir25Os75 nanoparticles due to optimized stability and conductivity, respectively. We propose that the Activity-Stability FactorASF is the key “metric” for determining the technological relevance of oxide-based anodic water electrolyzer catalysts.

  19. Direct, enantioselective α-alkylation of aldehydes using simple olefins.

    Science.gov (United States)

    Capacci, Andrew G; Malinowski, Justin T; McAlpine, Neil J; Kuhne, Jerome; MacMillan, David W C

    2017-11-01

    Although the α-alkylation of ketones has already been established, the analogous reaction using aldehyde substrates has proven surprisingly elusive. Despite the structural similarities between the two classes of compounds, the sensitivity and unique reactivity of the aldehyde functionality has typically required activated substrates or specialized additives. Here, we show that the synergistic merger of three catalytic processes-photoredox, enamine and hydrogen-atom transfer (HAT) catalysis-enables an enantioselective α-aldehyde alkylation reaction that employs simple olefins as coupling partners. Chiral imidazolidinones or prolinols, in combination with a thiophenol, iridium photoredox catalyst and visible light, have been successfully used in a triple catalytic process that is temporally sequenced to deliver a new hydrogen and electron-borrowing mechanism. This multicatalytic process enables both intra- and intermolecular aldehyde α-methylene coupling with olefins to construct both cyclic and acyclic products, respectively. With respect to atom and step-economy ideals, this stereoselective process allows the production of high-value molecules from feedstock chemicals in one step while consuming only photons.

  20. Development of tartaric acid derived chiral guanidines and their application to catalytic enantioselective α-hydroxylation of β-dicarbonyl compounds.

    Science.gov (United States)

    Zou, Liwei; Wang, Baomin; Mu, Hongfang; Zhang, Huanrui; Song, Yuming; Qu, Jingping

    2013-06-21

    A novel library of chiral guanidines featuring a tartaric acid skeleton was developed from diethyl l-tartrate. These guanidines are easily accessed with tunable steric and electronic properties. The utilities of the guanidines were highlighted by their ability to catalyze the α-hydroxylation of β-ketoesters and β-diketones with remarkable efficiency and excellent enantioselectivity.

  1. Activity of iridium-ruthenium and iridium-rhodium adsorption catalysts in decomposition of hydrogen peroxide

    Energy Technology Data Exchange (ETDEWEB)

    Zubovich, I A; Mikhaylov, V A; Migulina, N N [Yaroslavskij Politekhnicheskij Inst. (USSR)

    1976-06-01

    Experimental data for the activities of iridium-ruthenium and iridium-rhodium adsorption catalysts in the decomposition of hydrogen peroxide are considered and the results of magnetic susceptibility measurements are presented. It is concluded that surface structures (complexes) may be formed and that micro-electronic feaures play a role in heterogeneous catalysis.

  2. Cu-Catalyzed Asymmetric Allylic Alkylation of Phosphonates and Phosphine Oxides with Grignard Reagents

    NARCIS (Netherlands)

    Hornillos, Valentin; Perez, Manuel; Fananas-Mastral, Martin; Feringa, Ben L.

    An efficient and highly enantioselective copper-catalyzed allylic alkylation of phosphonates and phosphine oxides with Grignard reagents and Taniaphos or phosphoramidites as chiral ligands is reported. Transformation of these products leads to a variety of new phosphorus-containing chiral

  3. Asymmetric Chemoenzymatic Reductive Acylation of Ketones by a Combined Iron-Catalyzed Hydrogenation-Racemization and Enzymatic Resolution Cascade

    KAUST Repository

    El-Sepelgy, Osama

    2017-02-28

    A general and practical process for the conversion of prochiral ketones into the corresponding chiral acetates has been realized. An iron carbonyl complex is reported to catalyze the hydrogenation-dehydrogenation-hydrogenation of prochiral ketones. By merging the iron-catalyzed redox reactions with enantioselective enzymatic acylations a wide range of benzylic, aliphatic and (hetero)aromatic ketones, as well as diketones, were reductively acylated. The corresponding products were isolated with high yields and enantioselectivities. The use of an iron catalyst together with molecular hydrogen as the hydrogen donor and readily available ethyl acetate as acyl donor make this cascade process highly interesting in terms of both economic value and environmental credentials.

  4. Enantioselective synthesis of tetrafluorinated ribose and fructose.

    Science.gov (United States)

    Linclau, Bruno; Boydell, A James; Timofte, Roxana S; Brown, Kylie J; Vinader, Victoria; Weymouth-Wilson, Alexander C

    2009-02-21

    A perfluoroalkylidene lithium mediated cyclisation approach for the enantioselective synthesis of a tetrafluorinated aldose (ribose) and of a tetrafluorinated ketose (fructose), both in the furanose and in the pyranose form, is described.

  5. Kinetic investigation on enantioselective hydrolytic resolution of ...

    African Journals Online (AJOL)

    Kinetic investigation on enantioselective hydrolytic resolution of epichlorohydrin by crude epoxide hydrolase from domestic duck liver. X Ling, D Lu, J Wang, J Chen, L Ding, J Chen, H Chai, P Ouyang ...

  6. Enantioselective addition of nitrones to activated cyclopropanes.

    Science.gov (United States)

    Sibi, Mukund P; Ma, Zhihua; Jasperse, Craig P

    2005-04-27

    In this paper, we demonstrate the first examples of chiral Lewis acid catalysis in the formation of tetrahydro-1,2-oxazines with very high enantioselectivity starting with diactivated cyclopropanes and nitrones (>90% yields and ee). Reactions with racemic substituted cyclopropanes provide approximately 1:1 diastereomeric tetrahydro-1,2-oxazine products with high enantioselectivity. Mechanistic information for the formation of the tetrahydro-1,2-oxazines is also detailed.

  7. An ylide transformation of rhodium(I) carbene: enantioselective three-component reaction through trapping of rhodium(I)-associated ammonium ylides by β-nitroacrylates.

    Science.gov (United States)

    Ma, Xiaochu; Jiang, Jun; Lv, Siying; Yao, Wenfeng; Yang, Yang; Liu, Shunying; Xia, Fei; Hu, Wenhao

    2014-11-24

    The chiral Rh(I)-diene-catalyzed asymmetric three-component reaction of aryldiazoacetates, aromatic amines, and β-nitroacrylates was achieved to obtain γ-nitro-α-amino-succinates in good yields and with high diastereo- and enantioselectivity. This reaction is proposed to proceed through the enantioselective trapping of Rh(I)-associated ammonium ylides by nitroacrylates. This new transformation represents the first example of Rh(I)-carbene-induced ylide transformation. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. 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.

  9. Iron-57 and iridium-193 Moessbauer spectroscopic studies of supported iron-iridium catalysts

    International Nuclear Information System (INIS)

    Berry, F.J.; Jobson, S.

    1988-01-01

    57 Fe and 193 Ir Moessbauer spectroscopy shows that silica- and alumina-supported iron-iridium catalysts formed by calcination in air contain mixtures of small particle iron(III) oxide and iridium(IV) oxide. The iridium dioxide in both supported catalysts is reduced in hydrogen to metallic iridium. The α-Fe 2 O 3 in the silica supported materials is predominantly reduced in hydrogen to an iron-iridium alloy whilst in the alumina-supported catalyst the iron is stabilised by treatment in hydrogen as iron(II). Treatment of a hydrogen-reduced silica-supported iron catalyst in hydrogen and carbon monoxide is accompanied by the formation of iron carbides. Carbide formation is not observed when the iron-iridium catalysts are treated in similar atmospheres. The results from the bimetallic catalysts are discussed in terms of the hydrogenation of associatively adsorbed carbon monoxide and the selectivity of supported iron-iridium catalysts to methanol formation. (orig.)

  10. Preparative and mechanistic studies toward the rational development of catalytic, enantioselective selenoetherification reactions.

    Science.gov (United States)

    Denmark, Scott E; Kalyani, Dipannita; Collins, William R

    2010-11-10

    A systematic investigation into the Lewis base catalyzed, asymmetric, intramolecular selenoetherification of olefins is described. A critical challenge for the development of this process was the identification and suppression of racemization pathways available to arylseleniranium ion intermediates. This report details a thorough study of the influences of the steric and electronic modulation of the arylselenenyl group on the configurational stability of enantioenriched seleniranium ions. These studies show that the 2-nitrophenyl group attached to the selenium atom significantly attenuates the racemization of seleniranium ions. A variety of achiral Lewis bases catalyze the intramolecular selenoetherification of alkenes using N-(2-nitrophenylselenenyl)succinimide as the electrophile along with a Brønsted acid. Preliminary mechanistic studies suggest the intermediacy of ionic Lewis base-selenium(II) adducts. Most importantly, a broad survey of chiral Lewis bases revealed that 1,1'-binaphthalene-2,2'-diamine (BINAM)-derived thiophosphoramides catalyze the cyclization of unsaturated alcohols in the presence of N-(2-nitrophenylselenenyl)succinimide and methanesulfonic acid. A variety of cyclic seleno ethers were produced in good chemical yields and in moderate to good enantioselectivities, which constitutes the first catalytic, enantioselective selenofunctionalization of unactivated olefins.

  11. The Catalytic Enantioselective Total Synthesis of (+)‐Liphagal

    DEFF Research Database (Denmark)

    Day, Joshua J.; McFadden, Ryan M.; Virgil, Scott C.

    2011-01-01

    Ring a ding: The first catalytic enantioselective total synthesis of the meroterpenoid natural product (+)-liphagal is disclosed. The approach showcases a variety of technology including enantioselective enolate alkylation, a photochemical alkyne-alkene [2+2] reaction, microwaveassisted metal...

  12. A Tunable and Enantioselective Hetero-Diels-Alder Reaction Provides Access to Distinct Piperidinoyl Spirooxindoles.

    Science.gov (United States)

    Jayakumar, Samydurai; Louven, Kathrin; Strohmann, Carsten; Kumar, Kamal

    2017-12-11

    The active complexes of chiral N,N'-dioxide ligands with dysprosium and magnesium salts catalyze the hetero-Diels-Alder reaction between 2-aza-3-silyloxy-butadienes and alkylidene oxindoles to selectively form 3,3'- and 3,4'-piperidinoyl spirooxindoles, respectively, in very high yields and with excellent enantioselectivities. The exo-selective asymmetric cycloaddition successfully regaled the construction of sp 3 -rich and highly substituted natural-product-based spirooxindoles supporting many chiral centers, including contiguous all-carbon quaternary centers. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. 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.

  14. Iridium emissions from Hawaiian volcanoes

    International Nuclear Information System (INIS)

    Finnegan, D.L.; Zoller, W.H.; Miller, T.M.

    1988-01-01

    Particle and gas samples were collected at Mauna Loa volcano during and after its eruption in March and April, 1984 and at Kilauea volcano in 1983, 1984, and 1985 during various phases of its ongoing activity. In the last two Kilauea sampling missions, samples were collected during eruptive activity. The samples were collected using a filterpack system consisting of a Teflon particle filter followed by a series of 4 base-treated Whatman filters. The samples were analyzed by INAA for over 40 elements. As previously reported in the literature, Ir was first detected on particle filters at the Mauna Loa Observatory and later from non-erupting high temperature vents at Kilauea. Since that time Ir was found in samples collected at Kilauea and Mauna Loa during fountaining activity as well as after eruptive activity. Enrichment factors for Ir in the volcanic fumes range from 10,000 to 100,000 relative to BHVO. Charcoal impregnated filters following a particle filter were collected to see if a significant amount of the Ir was in the gas phase during sample collection. Iridium was found on charcoal filters collected close to the vent, no Ir was found on the charcoal filters. This indicates that all of the Ir is in particulate form very soon after its release. Ratios of Ir to F and Cl were calculated for the samples from Mauna Loa and Kilauea collected during fountaining activity. The implications for the KT Ir anomaly are still unclear though as Ir was not found at volcanoes other than those at Hawaii. Further investigations are needed at other volcanoes to ascertain if basaltic volcanoes other than hot spots have Ir enrichments in their fumes

  15. Iridium emissions from Hawaiian volcanoes

    Science.gov (United States)

    Finnegan, D. L.; Zoller, W. H.; Miller, T. M.

    1988-01-01

    Particle and gas samples were collected at Mauna Loa volcano during and after its eruption in March and April, 1984 and at Kilauea volcano in 1983, 1984, and 1985 during various phases of its ongoing activity. In the last two Kilauea sampling missions, samples were collected during eruptive activity. The samples were collected using a filterpack system consisting of a Teflon particle filter followed by a series of 4 base-treated Whatman filters. The samples were analyzed by INAA for over 40 elements. As previously reported in the literature, Ir was first detected on particle filters at the Mauna Loa Observatory and later from non-erupting high temperature vents at Kilauea. Since that time Ir was found in samples collected at Kilauea and Mauna Loa during fountaining activity as well as after eruptive activity. Enrichment factors for Ir in the volcanic fumes range from 10,000 to 100,000 relative to BHVO. Charcoal impregnated filters following a particle filter were collected to see if a significant amount of the Ir was in the gas phase during sample collection. Iridium was found on charcoal filters collected close to the vent, no Ir was found on the charcoal filters. This indicates that all of the Ir is in particulate form very soon after its release. Ratios of Ir to F and Cl were calculated for the samples from Mauna Loa and Kilauea collected during fountaining activity. The implications for the KT Ir anomaly are still unclear though as Ir was not found at volcanoes other than those at Hawaii. Further investigations are needed at other volcanoes to ascertain if basaltic volcanoes other than hot spots have Ir enrichments in their fumes.

  16. Predictable and Regioselective Insertion of Internal Unsymmetrical Alkynes in Rhodium-Catalyzed Cycloadditions with Alkenyl Isocyanates

    Science.gov (United States)

    Friedman, Rebecca Keller; Rovis, Tomislav

    2009-01-01

    A regioselective, rhodium-catalyzed cycloaddition between a variety of internal, unsymmetrical alkynes is described. We document the impact of both steric and electronic properties of the alkyne on reaction course, efficiency and enantioselectivity. The substituent that better stabilizes a positive charge or the larger group, all else being equal, inserts distal to the carbonyl moiety in a predictable and controllable fashion. The reaction scope is broad and the enantioselectivities are high, providing an ‘instruction manual’ for substrate choice when utilizing this reaction as a synthetic tool. PMID:19569692

  17. Synthesis of l-threitol-based crown ethers and their application as enantioselective phase transfer catalyst in Michael additions.

    Science.gov (United States)

    Rapi, Zsolt; Nemcsok, Tamás; Pálvölgyi, Ádám; Keglevich, György; Grün, Alajos; Bakó, Péter

    2017-06-01

    A few new l-threitol-based lariat ethers incorporating a monoaza-15-crown-5 unit were synthesized starting from diethyl l-tartrate. These macrocycles were used as phase transfer catalysts in asymmetric Michael addition reactions under mild conditions to afford the adducts in a few cases in good to excellent enantioselectivities. The addition of 2-nitropropane to trans-chalcone, and the reaction of diethyl acetamidomalonate with β-nitrostyrene resulted in the chiral Michael adducts in good enantioselectivities (90% and 95%, respectively). The substituents of chalcone had a significant impact on the yield and enantioselectivity in the reaction of diethyl acetoxymalonate. The highest enantiomeric excess (ee) values (99% ee) were measured in the case of 4-chloro- and 4-methoxychalcone. The phase transfer catalyzed cyclopropanation reaction of chalcone and benzylidene-malononitriles using diethyl bromomalonate as the nucleophile (MIRC reaction) was also developed. The corresponding chiral cyclopropane diesters were obtained in moderate to good (up to 99%) enantioselectivities in the presence of the threitol-based crown ethers. © 2017 Wiley Periodicals, Inc.

  18. Enantioselective Biotransformation of Chiral Persistent Organic Pollutants.

    Science.gov (United States)

    Zhang, Ying; Ye, Jing; Liu, Min

    2017-01-01

    Enantiomers of chiral compounds commonly undergo enantioselective transformation in most biologically mediated processes. As chiral persistent organic pollutants (POPs) are extensively distributed in the environment, differences between enantiomers in biotransformation should be carefully considered to obtain exact enrichment and specific health risks. This review provides an overview of in vivo biotransformation of chiral POPs currently indicated in the Stockholm Convention and their chiral metabolites. Peer-reviewed journal articles focused on the research question were thoroughly searched. A set of inclusion and exclusion criteria were developed to identify relevant studies. We mainly compared the results from different animal models under controlled laboratory conditions to show the difference between enantiomers in terms of distinct transformation potential. Interactions with enzymes involved in enantioselective biotransformation, especially cytochrome P450 (CYP), were discussed. Further research areas regarding this issue were proposed. Limited evidence for a few POPs has been found in 30 studies. Enantioselective biotransformation of α-hexachlorocyclohexane (α-HCH), chlordane, dichlorodiphenyltrichloroethane (DDT), heptachlor, hexabromocyclododecane (HBCD), polychlorinated biphenyls (PCBs), and toxaphene, has been investigated using laboratory mammal, fish, bird, and worm models. Tissue and excreta distributions, as well as bioaccumulation and elimination kinetics after administration of racemate and pure enantiomers, have been analyzed in these studies. Changes in enantiomeric fractions have been considered as an indicator of enantioselective biotransformation of chiral POPs in most studies. Results of different laboratory animal models revealed that chiral POP biotransformation is seriously affected by chirality. Pronounced results of species-, tissue-, gender-, and individual-dependent differences are observed in in vivo biotransformation of chiral POPs

  19. Iridium-192 sources production for brachytherapy use

    International Nuclear Information System (INIS)

    Rostelato, Maria Elisa Chuery Martins

    1997-01-01

    The incidence of cancer increases every year in Brazil and turns out to be one of the most important causes of mortality. Some of the patients are treated with brachytherapy, a form of lesion treatment which is based on the insertion of sources into tumors, in this particular case, activated iridium wires. During this process, the ionizing radiation efficiently destroys the malignant cells. These iridium wires have a nucleus made out of an iridium-platinum alloy 20-30/70-80 of 0,1 mm in diameter either coated by platinum or encased in a platinum tube. The technique consists in irradiating the wire in the reactor neutron flux in order to produce iridium-192. The linear activity goes from 1 mCi/cm to 4 mCi/cm and the basic characteristic, which is required, is the homogeneity of the activation along the wire. It should not present a dispersion exceeding 5% on a wire measuring 50 cm in length, 0.5 mm or 0.3 mm in diameter. Several experiments were carried out in order to define the activation parameters. Wires from different origins were analyzed. It was concluded that United States of America and France wires were found to be perfectly adequate for brachytherapy purposes and have therefore been sent to specialized hospitals and successfully applied to cancer patients. Considering that the major purpose of this work is to make this product more accessible in Brazil, at a cost reflecting the Brazilian reality, the IPEN is promoting the preparation of iridium-192 sources to be used in brachytherapy, on a national level. (author)

  20. Welding of iridium heat source capsule components

    International Nuclear Information System (INIS)

    Mustaleski, T.M.; Yearwood, J.C.; Burgan, C.E.; Green, L.A.

    1991-01-01

    Interplanetary spacecraft have long used radioisotope thermoelectric generators (RTG) to produce power for instrumentation. These RTG produce electrical energy from the heat generated through the radioactive decay of plutonium-238. The plutonium is present as a ceramic pellet of plutonium oxide. The pellet is encapsulated in a containment shell of iridium. Iridium is the material of choice for these capsules because of its compatibility with the plutonium dioxide. The high-energy beam welding (electron beam and laser) processes used in the fabrication of the capsules has not been published. These welding procedures were originally developed at the Mound Laboratories and have been adapted for use at the Oak Ridge Y-12 Plant. The work involves joining of thin material in small sizes to exacting tolerances. There are four different electron beam welds on each capsule, with one procedure being used in three locations. There is also a laser weld used to seal the edges of a sintered frit assembly. An additional electron beam weld is also performed to seal each of the iridium blanks in a stainless steel waster sheet prior to forming. In the transfer of these welding procedures from one facility to another, a number of modifications were necessary. These modifications are discussed in detail, as well as the inherent problems in making welds in material which is only 0.005 in. thick. In summary, the paper discusses the welding of thin components of iridium using the high energy beam processes. While the peculiarities of iridium are pertinent to the discussion, much of the information is of general interest to the users of these processes. This is especially true of applications involving thin materials and high-precision assemblies

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

    Directory of Open Access Journals (Sweden)

    Magnus Rueping

    2012-10-01

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

  2. Ru/Me-BIPAM-Catalyzed Asymmetric Addition of Arylboronic Acids to Aliphatic Aldehydes and α-Ketoesters

    Directory of Open Access Journals (Sweden)

    Momoko Watanabe

    2011-06-01

    Full Text Available A ruthenium-catalyzed asymmetric arylation of aliphatic aldehydes and α-ketoesters with arylboronic acids has been developed, giving chiral alkyl(arylmethanols and α-hydroxy esters in good yields. The use of a chiral bidentate phosphoramidite ligand (Me-BIPAM achieved excellent enantioselectivities.

  3. (Salen)Ti(Ⅳ)-Catalyzed Asymmetric Ring-opening of meso Epoxides Using Dithiophosphorus Acid as the Nucleophile

    Institute of Scientific and Technical Information of China (English)

    Zheng Hong ZHOU; Zhao Ming LI; Bing LIU; Kang Ying LI; Li Xin WANG; Guo Feng ZHAO; Qi Lin ZHOU; Chu Chi TANG

    2006-01-01

    The asymmetric ring-opening of epoxides with dithiophosphorus acids catalyzed by a (salen)Ti(Ⅳ) complex formed in situ from the reaction of Ti(OPr-i)4 and the chiral Schiff base derived from (1R,2R)-(+)-diaminocyclohexane was realized. The resulting products were obtained with low to good enantioselectivity (up to 73% ee).

  4. PipPhos and MorfPhos : Privileged monodentate phosphoramidite ligands for rhodium-catalyzed asymmetric hydrogenation

    NARCIS (Netherlands)

    Bernsmann, Heiko; van den Berg, M; Hoen, Robert; Minnaard, AJ; Mehler, G; Reetz, MT; De Vries, JG; Feringa, BL

    2005-01-01

    A library of 20 monodentate phosphoramidite ligands has been prepared and applied in rhodium-catalyzed asymmetric hydrogenation. This resulted in the identification of two ligands, PipPhos and MorfPhos, that afford excellent and in several cases unprecedented enantioselectivities in the

  5. Enantioselective inhibition of carprofen towards UDP-glucuronosyltransferase (UGT) 2B7.

    Science.gov (United States)

    Fang, Zhong-Ze; Wang, Haina; Cao, Yun-Feng; Sun, Dong-Xue; Wang, Li-Xuan; Hong, Mo; Huang, Ting; Chen, Jian-Xing; Zeng, Jia

    2015-03-01

    UDP-glucuronosyltransferases (UGTs)-catalyzed glucuronidation conjugation reaction plays an important role in the elimination of many important clinical drugs and endogenous substances. The present study aims to investigate the enantioselective inhibition of carprofen towards UGT isoforms. In vitro a recombinant UGT isoforms-catalyzed 4-methylumbelliferone (4-MU) glucuronidation incubation mixture was used to screen the inhibition potential of (R)-carprofen and (S)-carprofen towards multiple UGT isoforms. The results showed that (S)-carprofen exhibited stronger inhibition potential than (R)-carprofen towards UGT2B7. However, no significant difference was observed for the inhibition of (R)-carprofen and (S)-carprofen towards other UGT isoforms. Furthermore, the inhibition kinetic behavior was compared for the inhibition of (S)-carprofen and (R)-carprofen towards UGT2B7. A Lineweaver-Burk plot showed that both (S)-carprofen and (R)-carprofen exhibited competitive inhibition towards UGT2B7-catalyzed 4-MU glucuronidation. The inhibition kinetic parameter (Ki ) was calculated to be 7.0 μM and 31.1 μM for (S)-carprofen and (R)-carprofen, respectively. Based on the standard for drug-drug interaction, the threshold for (S)-carprofen and (R)-carprofen to induce a drug-drug interaction is 0.7 μM and 3.1 μM, respectively. In conclusion, enantioselective inhibition of carprofen towards UDP-glucuronosyltransferase (UGT) 2B7 was demonstrated in the present study. Using the in vitro inhibition kinetic parameter, the concentration threshold of (S)-carprofen and (R)-carprofen to possibly induce the drug-drug interaction was obtained. Therefore, clinical monitoring of the plasma concentration of (S)-carprofen is more important than (R)-carprofen to avoid a possible drug-drug interaction between carprofen and the drugs mainly undergoing UGT2B7-catalyzed metabolism. © 2014 Wiley Periodicals, Inc.

  6. Effective Area and Charge Density of Iridium Oxide Neural Electrodes

    International Nuclear Information System (INIS)

    Harris, Alexander R.; Paolini, Antonio G.; Wallace, Gordon G.

    2017-01-01

    The effective electrode area and charge density of iridium metal and anodically activated iridium has been measured by optical and electrochemical techniques. The degree of electrode activation could be assessed by changes in electrode colour. The reduction charge, activation charge, number of activation pulses and charge density were all strongly correlated. Activated iridium showed slow electron transfer kinetics for reduction of a dissolved redox species. At fast voltammetric scan rates the linear diffusion electroactive area was unaffected by iridium activation. At slow voltammetric scan rates, the steady state diffusion electroactive area was reduced by iridium activation. The steady state current was consistent with a ring electrode geometry, with lateral resistance reducing the electrode area. Slow electron transfer on activated iridium would require a larger overpotential to reduce or oxidise dissolved species in tissue, limiting the electrodes charge capacity but also reducing the likelihood of generating toxic species in vivo.

  7. The Catalytic Enantioselective Total Synthesis of (+)-Liphagal

    KAUST Repository

    Day, Joshua J.

    2011-06-10

    Ring a ding: The meroterpenoid natural product (+)-liphagal has been synthesized enantioselectively in 19 steps from commercially available materials. The trans-homodecalin system was achieved by ring expansion followed by stereoselective hydrogenation. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. The Catalytic Enantioselective Total Synthesis of (+)-Liphagal

    KAUST Repository

    Day, Joshua J.; McFadden, Ryan M.; Virgil, Scott C.; Kolding, Helene; Alleva, Jennifer L.; Stoltz, Brian M.

    2011-01-01

    Ring a ding: The meroterpenoid natural product (+)-liphagal has been synthesized enantioselectively in 19 steps from commercially available materials. The trans-homodecalin system was achieved by ring expansion followed by stereoselective hydrogenation. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Enantioselective properties of induced lipases from Geotrichum

    Czech Academy of Sciences Publication Activity Database

    Zarevúcka, Marie; Kejík, Z.; Šaman, David; Wimmer, Zdeněk; Demnerová, K.

    2005-01-01

    Roč. 37, - (2005), s. 481-486 ISSN 0141-0229 R&D Projects: GA MŠk(CZ) OC D30.001; GA MŠk(CZ) OC D13.10 Institutional research plan: CEZ:AV0Z40550506 Keywords : Geotrichum * lipase * enantioselectivity Subject RIV: CC - Organic Chemistry Impact factor: 1.705, year: 2005

  10. Enantioselective pharmacokinetics of sibutramine in rat.

    Science.gov (United States)

    Noh, Keumhan; Bae, Kyoungjin; Min, Bokyoung; Kim, Eunyoung; Kwon, Kwang-il; Jeong, Taecheon; Kang, Wonku

    2010-02-01

    Racemic sibutramine is widely used to treat obesity owing to its inhibition of serotonin and noradrenaline reuptake in synapses. Although the enantioselective effects of sibutramine and its two active desmethyl-metabolites, monodesmethylsibutramine (MDS) and didesmethylsibutramine (DDS), on anorexia and energy expenditure have been elucidated, the enantioselective pharmacokinetics of sibutramine are still unclear. Therefore, we aimed to characterize the enantioselective pharmacokinetics of sibutramine and its metabolites in plasma and urine following an intravenous and a single oral administration of sibutramine in rats. The absolute bioavailability of sibutramine was only about 7%. The pharmacologically less effective S-isomer of DDS was predominant in the plasma: the C ( max ) and the AUC ( inf ) were 28 and 30 times higher than those of the R-isomer, respectively (psibutramine metabolites MDS and DDS were present at lower concentrations, owing to their rapid biotransformation to hydroxylated and/or carbamoylglucuronized forms and their faster excretion in the urine. The present study is the first to elucidate the enantioselective pharmacokinetics of sibutramine in rats.

  11. Impedance analysis of nanostructured iridium oxide electrocatalysts

    International Nuclear Information System (INIS)

    Sunde, Svein; Lervik, Ingrid Anne; Tsypkin, Mikhail; Owe, Lars-Erik

    2010-01-01

    Impedance data were collected for nanostructured iridium oxide (NIROF) at potentials below those at which the oxygen evolution reaction commences. The measurements included thin oxide films covered by a protective Nafion TM layer and thicker composite Nafion TM -oxide electrodes. The time constants for the low-frequency diffusion process were approximately the same for both types of electrodes, indicating diffusion in individual particles in the porous electrode rather than across the film. The diffusion process involves trapping of the diffusion species. The impedance data indicated that there were no significant variations in conductivity of the oxides with potential, as opposed to what appears to be the case for anodically formed iridium oxide films (AIROF). This is interpreted to reflect differences in electronic structure between NIROF and AIROF.

  12. Enantioselectivity in environmental risk assessment of modern chiral pesticides

    International Nuclear Information System (INIS)

    Ye Jing; Zhao Meirong; Liu Jing; Liu Weiping

    2010-01-01

    Chiral pesticides comprise a new and important class of environmental pollutants nowadays. With the development of industry, more and more chiral pesticides will be introduced into the market. But their enantioselective ecotoxicology is not clear. Currently used synthetic pyrethroids, organophosphates, acylanilides, phenoxypropanoic acids and imidazolinones often behave enantioselectively in agriculture use and they always pose unpredictable enantioselective ecological risks on non-target organisms or human. It is necessary to explore the enantioselective toxicology and ecological fate of these chiral pesticides in environmental risk assessment. The enantioselective toxicology and the fate of these currently widely used pesticides have been discussed in this review article. - Chiral pesticides could pose unpredictable enantioselective toxicity on non-target organisms.

  13. A general enantioselective route to the chamigrene natural product family

    KAUST Repository

    White, David E.

    2010-06-01

    Described in this report is an enantioselective route toward the chamigrene natural product family. The key disconnections in our synthetic approach include sequential enantioselective decarboxylative allylation and ring-closing olefin metathesis to form the all-carbon quaternary stereocenter and spirocyclic core present in all members of this class of compounds. The generality of this strategy is demonstrated by the first total syntheses of elatol and the proposed structure of laurencenone B, as well as the first enantioselective total syntheses of laurencenone C and α-chamigrene. A brief exploration of the substrate scope of the enantioselective decarboxylative allylation/ring-closing metathesis sequence with fully substituted vinyl chlorides is also presented.

  14. A general enantioselective route to the chamigrene natural product family

    KAUST Repository

    White, David E.; Stewart, Ian C.; Seashore-Ludlow, Brinton A.; Grubbs, Robert H.; Stoltz, Brian M.

    2010-01-01

    Described in this report is an enantioselective route toward the chamigrene natural product family. The key disconnections in our synthetic approach include sequential enantioselective decarboxylative allylation and ring-closing olefin metathesis to form the all-carbon quaternary stereocenter and spirocyclic core present in all members of this class of compounds. The generality of this strategy is demonstrated by the first total syntheses of elatol and the proposed structure of laurencenone B, as well as the first enantioselective total syntheses of laurencenone C and α-chamigrene. A brief exploration of the substrate scope of the enantioselective decarboxylative allylation/ring-closing metathesis sequence with fully substituted vinyl chlorides is also presented.

  15. Z-Selective iridium-catalyzed cross-coupling of allylic carbonates and α-diazo esters† †Electronic supplementary information (ESI) available: Full procedures, computational details and characterization data. See DOI: 10.1039/c7sc04283c

    Science.gov (United States)

    Thomas, Bryce N.; Moon, Patrick J.; Yin, Shengkang; Brown, Alex

    2017-01-01

    A well-defined Ir–allyl complex catalyzes the Z-selective cross-coupling of allyl carbonates with α-aryl diazo esters. The process overrides the large thermodynamic preference for E-products typically observed in metal-mediated coupling reactions to enable the synthesis of Z,E-dieneoates in good yield with selectivities consistently approaching or greater than 90 : 10. This transformation represents the first productive merger of Ir–carbene and Ir–allyl species, which are commonly encountered intermediates in allylation and cyclopropanation/E–H insertion catalysis. Potentially reactive functional groups (aryl halides, ketones, nitriles, olefins, amines) are tolerated owing to the mildness of reaction conditions. Kinetic analysis of the reaction suggests oxidative addition of the allyl carbonate to an Ir-species is rate-determining. Mechanistic studies uncovered a pathway for catalyst activation mediated by NEt3. PMID:29629093

  16. Simultaneous iridium catalysed oxidation and enzymatic reduction employing orthogonal reagents

    NARCIS (Netherlands)

    Mutti, Francesco G.; Orthaber, Andreas; Schrittwieser, Joerg H.; Vries, Johannes G. de; Pietschnig, Rudolf; Kroutil, Wolfgang

    2010-01-01

    An iridium catalysed oxidation was coupled concurrently to an asymmetric biocatalytic reduction in one-pot; thus it was shown for the first time that iridium- and alcohol dehydrogenase-catalysed redox reactions are compatible. As a model system racemic chlorohydrins were transformed to

  17. pH-sensor properties of electrochemically grown iridium oxide

    NARCIS (Netherlands)

    Olthuis, Wouter; Robben, M.A.M.; Bergveld, Piet; Bos, M.; van der Linden, W.E.

    1990-01-01

    The open-circuit potential of an electrochemically grown iridium oxide film is measured and shows a pH sensitivity between −60 and −80 mV/pH. This sensitivity is found to depend on the state of oxidation of the iridium oxide film; for a higher state of oxidation (or more of the oxide in the high

  18. Weldability of general purpose heat source new-process iridium

    International Nuclear Information System (INIS)

    Kanne, W.R.

    1987-01-01

    Weldability tests on General Purpose Heat Source (GPHS) iridium capsules showed that a new iridium fabrication process reduced susceptibility to underbead cracking. Seventeen capsules were welded (a total of 255 welds) in four categories and the number of cracks in each weld was measured

  19. Vancomycin Molecular Interactions: Antibiotic and Enantioselective Mechanisms

    Science.gov (United States)

    Ward, Timothy J.; Gilmore, Aprile; Ward, Karen; Vowell, Courtney

    Medical studies established that vancomycin and other related macrocyclic antibiotics have an enhanced antimicrobial activity when they are associated as dimers. The carbohydrate units attached to the vancomycin basket have an essential role in the dimerization reaction. Covalently synthesized dimers were found active against vancomycin-resistant bacterial strains. A great similarity between antibiotic potential and enantioselectivity was established. A covalent vancomycin dimer was studied in capillary electrophoresis producing excellent chiral separation of dansyl amino acids. Balhimycin is a macrocyclic glycopeptide structurally similar to vancomycin. The small differences are, however, responsible for drastic differences in enantioselectivity in the same experimental conditions. Contributions from studies examining vancomycin's mechanism for antimicrobial activity have substantially aided our understanding of its mechanism in chiral recognition.

  20. 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.

  1. Beyond Iron: Iridium-Containing P450 Enzymes for Selective Cyclopropanations of Structurally Diverse Alkenes

    International Nuclear Information System (INIS)

    Key, Hanna M.; Dydio, Paweł; Liu, Zhennan

    2017-01-01

    Enzymes catalyze organic transformations with exquisite levels of selectivity, including chemoselectivity, stereoselectivity, and substrate selectivity, but the types of reactions catalyzed by enzymes are more limited than those of chemical catalysts. Thus, the convergence of chemical catalysis and biocatalysis can enable enzymatic systems to catalyze abiological reactions with high selectivity. Recently, we disclosed artificial enzymes constructed from the apo form of heme proteins and iridium porphyrins that catalyze the insertion of carbenes into a C-H bond. Here, we postulated that the same type of Ir(Me)-PIX enzymes could catalyze the cyclopropanation of a broad range of alkenes with control of multiple modes of selectivity. Here, we report the evolution of artificial enzymes that are highly active and highly stereoselective for the addition of carbenes to a wide range of alkenes. These enzymes catalyze the cyclopropanation of terminal and internal, activated and unactivated, electron-rich and electron-deficient, conjugated and nonconjugated alkenes. In particular, Ir(Me)-PIX enzymes derived from CYP119 catalyze highly enantio- and diastereoselective cyclopropanations of styrene with ±98% ee, > 70:1 dr, > 75% yield, and ~10,000 turnovers (TON), as well as 1,2-disubstituted styrenes with up to 99% ee, 35:1 dr, and 54% yield. Moreover, Ir(Me)-PIX enzymes catalyze cyclopropanation of internal, unactivated alkenes with up to 99% stereoselectivity, 76% yield, and 1300 TON. They also catalyze cyclopropanation of natural products with diastereoselectivities that are complementary to those attained with standard transition metal catalysts. Finally, Ir(Me)-PIX P450 variants react with substrate selectivity that is reminiscent of natural enzymes; they react preferentially with less reactive internal alkenes in the presence of more reactive terminal alkenes. Altogether, the studies reveal the suitability of Ir-containing P450s to combine the broad reactivity and

  2. Iridium Interfacial Stack - IrIS

    Science.gov (United States)

    Spry, David

    2012-01-01

    Iridium Interfacial Stack (IrIS) is the sputter deposition of high-purity tantalum silicide (TaSi2-400 nm)/platinum (Pt-200 nm)/iridium (Ir-200 nm)/platinum (Pt-200 nm) in an ultra-high vacuum system followed by a 600 C anneal in nitrogen for 30 minutes. IrIS simultaneously acts as both a bond metal and a diffusion barrier. This bondable metallization that also acts as a diffusion barrier can prevent oxygen from air and gold from the wire-bond from infiltrating silicon carbide (SiC) monolithically integrated circuits (ICs) operating above 500 C in air for over 1,000 hours. This TaSi2/Pt/Ir/Pt metallization is easily bonded for electrical connection to off-chip circuitry and does not require extra anneals or masking steps. There are two ways that IrIS can be used in SiC ICs for applications above 500 C: it can be put directly on a SiC ohmic contact metal, such as Ti, or be used as a bond metal residing on top of an interconnect metal. For simplicity, only the use as a bond metal is discussed. The layer thickness ratio of TaSi2 to the first Pt layer deposited thereon should be 2:1. This will allow Si from the TaSi2 to react with the Pt to form Pt2Si during the 600 C anneal carried out after all layers have been deposited. The Ir layer does not readily form a silicide at 600 C, and thereby prevents the Si from migrating into the top-most Pt layer during future anneals and high-temperature IC operation. The second (i.e., top-most) deposited Pt layer needs to be about 200 nm to enable easy wire bonding. The thickness of 200 nm for Ir was chosen for initial experiments; further optimization of the Ir layer thickness may be possible via further experimentation. Ir itself is not easily wire-bonded because of its hardness and much higher melting point than Pt. Below the iridium layer, the TaSi2 and Pt react and form desired Pt2Si during the post-deposition anneal while above the iridium layer remains pure Pt as desired to facilitate easy and strong wire-bonding to the Si

  3. Problems associated with iridium-192 wire implants

    International Nuclear Information System (INIS)

    Arnott, S.J.; Law, J.; Ash, D.; Flynn, A.; Paine, C.H.; Durrant, K.R.; Barber, C.D.; Dixon-Brown, A.

    1985-01-01

    Three incidents are reported, from different radiotherapy centres, in which an implanted iridium-192 wire remained in the tissues of a patient after withdrawal of the plastic tubing in which it was contained. In each case the instrument used to cut the wire had probably formed a hook on the end of the wire which caused it to catch in the tissues. Detailed recommendations are made for avoiding such incidents in the future, the most important of which is that the patient should be effectively monitored after the supposed removal of all radioactive sources. (author)

  4. Fluxional additives: a second generation control in enantioselective catalysis.

    Science.gov (United States)

    Sibi, Mukund P; Manyem, Shankar; Palencia, Hector

    2006-10-25

    The concept of "fluxional additives", additives that can adopt enantiomeric conformations depending on the chiral information in the ligand, is demonstrated in enantioselective Diels-Alder and nitrone cycloaddition reactions. The additive design is modular, and diverse structures are accessible in three steps. Chiral Lewis acids from main group and transition metals show enhancements in enantioselectivity in the presence of these additives.

  5. Tin-free enantioselective radical reactions using silanes.

    Science.gov (United States)

    Sibi, Mukund P; Yang, Yong-Hua; Lee, Sunggi

    2008-12-04

    Readily available hexyl silane is an excellent choice as a H-atom donor and a chain carrier in Lewis acid mediated enantioselective radical reactions. Conjugate radical additions to alpha,beta-unsaturated imides at room temperature proceed in good yields and excellent enantioselectivities.

  6. Chiral amides via copper-catalysed enantioselective conjugate addition

    NARCIS (Netherlands)

    Schoonen, Anne K.; Fernández-Ibáñez, M. Ángeles; Fañanás-Mastral, Martín; Teichert, Johannes F.; Feringa, Bernard

    2014-01-01

    A highly enantioselective one pot procedure for the synthesis of beta-substituted amides was developed starting from the corresponding alpha,beta-unsaturated esters. This new methodology is based on the copper-catalysed enantioselective conjugate addition of Grignard reagents to

  7. Asymmetric Construction of Benzindoloquinolizidine: Application of An Organocatalytic Enantioselective Conjugate Addition-Cyclization Cascade Reaction

    International Nuclear Information System (INIS)

    Kim, Cheolwoong; Seo, Seung Woo; Lee, Yona; Kim, Sunggon

    2014-01-01

    We have developed the synthetic methodology of enantioenriched benzindoloquinolizidines based on the organocatalytic enantioselective conjugate addition-cyclization cascade reaction of o-N-(3-indoleacetyl)amino-cinnamaldehydes with malonates followed by an acid-catalyzed intramolecular Pictet-Spengler type cyclization. The asymmetric reaction using diphenylprolinol TMS ether as an organocatalyst produces the desired products with good to excellent yields and high enantioselectivities (up to 98% ee). The evaluation of the applications of this synthetic methodology for generating enantioenriched benzindolo-quinolizidines and studies on the biological activity of these compounds against human prostate cancer in particular are now in progress. Results of these studies will be presented in due course. Many new types of chemical reactions have been developed to facilitate easier synthesis of complex compounds. Among the strategies, domino reactions, which have been utilized for the efficient and stereoselective construction of complex molecules from simple precursors in a single process, are widely used due to their high synthetic efficiency by reducing both the number of synthetic operation required and the quantities of chemicals and solvents used

  8. Influence of gasoline inhalation on the enantioselective pharmacokinetics of fluoxetine in rats.

    Science.gov (United States)

    Cardoso, Juciane Lauren Cavalcanti; Lanchote, Vera Lucia; Pereira, Maria Paula Marques; Capela, Jorge Manuel Vieira; Lepera, José Salvador

    2013-03-01

    Fluoxetine is used clinically as a racemic mixture of (+)-(S) and (-)-(R) enantiomers for the treatment of depression. CYP2D6 catalyzes the metabolism of both fluoxetine enantiomers. We aimed to evaluate whether exposure to gasoline results in CYP2D inhibition. Male Wistar rats exposed to filtered air (n = 36; control group) or to 600 ppm of gasoline (n = 36) in a nose-only inhalation exposure chamber for 6 weeks (6 h/day, 5 days/week) received a single oral 10-mg/kg dose of racemic fluoxetine. Fluoxetine enantiomers in plasma samples were analyzed by a validated analytical method using LC-MS/MS. The separation of fluoxetine enantiomers was performed in a Chirobiotic V column using as the mobile phase a mixture of ethanol:ammonium acetate 15 mM. Higher plasma concentrations of the (+)-(S)-fluoxetine enantiomer were found in the control group (enantiomeric ratio AUC((+)-(S)/(-)-(R)) = 1.68). In animals exposed to gasoline, we observed an increase in AUC(0-∞) for both enantiomers, with a sharper increase seen for the (-)-(R)-fluoxetine enantiomer (enantiomeric ratio AUC((+)-(S)/(-)-(R)) = 1.07), resulting in a loss of enantioselectivity. Exposure to gasoline was found to result in the loss of enantioselectivity of fluoxetine, with the predominant reduction occurring in the clearance of the (-)-(R)-fluoxetine enantiomer (55% vs. 30%). Copyright © 2013 Wiley Periodicals, Inc.

  9. A Mixed-Ligand Chiral Rhodium(II) Catalyst Enables the Enantioselective Total Synthesis of Piperarborenine B.

    Science.gov (United States)

    Panish, Robert A; Chintala, Srinivasa R; Fox, Joseph M

    2016-04-11

    A novel, mixed-ligand chiral rhodium(II) catalyst, Rh2(S-NTTL)3(dCPA), has enabled the first enantioselective total synthesis of the natural product piperarborenine B. A crystal structure of Rh2(S-NTTL)3(dCPA) reveals a "chiral crown" conformation with a bulky dicyclohexylphenyl acetate ligand and three N-naphthalimido groups oriented on the same face of the catalyst. The natural product was prepared on large scale using rhodium-catalyzed bicyclobutanation/ copper-catalyzed homoconjugate addition chemistry in the key step. The route proceeds in ten steps with an 8% overall yield and 92% ee. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Iridium Catalysis: Reductive Conversion of Glucan to Xylan

    DEFF Research Database (Denmark)

    Pedersen, Martin Jæger; Madsen, Robert; Clausen, Mads Hartvig

    2018-01-01

    By using iridium catalysed dehydrogenative decarbonylation, we converted a partly protected cellobioside into a fully protected xylobioside. We demonstrate good yields with two different aromatic ester protecting groups. The resulting xylobioside was directly used as glycosyl donor in further...

  11. Laser welding parameters for manufacturing iridium-192 (Ir-192) source

    International Nuclear Information System (INIS)

    Anung Pujiyanto; Moch Subechi; Hotman Lubis; Diandono KY

    2013-01-01

    Number of cervical cancer patients in Indonesia is growing every year. One of cervical cancer treatment was fairly effective use brachytherapy treatment with radioisotope sources of iridium-192. Manufacturing of iridium sources for brachytherapy can be done by incorporating the iridium-192 into stainless steel microcapsules then welding using laser welder which the quality of the welding of iridium source (Ir-192) was determined by the welding parameters such as full power, energy frequency, average power and speed. Based on the result of leakage test using pressure -20 inch Hg and tensile test 2.5 bar showed the welding parameters III and IV did not have leakage and damaged. So that parameters III and IV are recommended to be applied to Ir-192 HDR's source. (author)

  12. Growth and characterization of iridium dioxide nanorods

    International Nuclear Information System (INIS)

    Chen, R.S.; Huang, Y.S.; Liang, Y.M.; Tsai, D.S.; Tiong, K.K.

    2004-01-01

    Conductive iridium dioxide (IrO 2 ) nanorods have been successfully grown on the Si(1 0 0) substrates via metalorganic chemical vapor deposition (MOCVD). A wedge-shaped morphology and naturally formed sharp tips are observed for IrO 2 nanorods using field-emission scanning electron microscopy (FESEM). High-resolution transmission electron microscopy (TEM) image and electron diffraction pattern show the growth of IrO 2 nanorods preferentially along c-axis. Structure and composition of IrO 2 nanorods have also been characterized using the techniques of Raman spectroscopy and X-ray photoelectron spectroscopy (XPS), respectively. It is noted that the IrO 2 nanorods are self-mediated instead of the conventional vapor-liquid-solid (VLS) approach or catalyst-mediated method

  13. Iridium complexes for the application of photodynamic therapy

    Directory of Open Access Journals (Sweden)

    SHI Min

    2015-10-01

    Full Text Available Photodynamic therapy can destruct tumor cells by singlet oxygen which is generated via a photodynamic reaction of the photosensitizer under a specfic excitation wavelength.Due to the heavy atom effect of metal iridium,iridiumcomplexes are excited by suitable light and then reach their excited triple state through intersystem crossing.The excited iridium complexes transfer energy to oxygen molecules to produce singlet oxygen for photodynamic therapy.

  14. Excess Substrate is a Spectator Ligand in a Rhodium-Catalyzed Asymmetric [2+2+2] Cycloaddition of Alkenyl Isocyanates with Tolanes

    Science.gov (United States)

    Oinen, Mark Emil; Yu, Robert T.; Rovis, Tomislav

    2009-01-01

    Excess substrate has been identified as an unintended spectator ligand affecting enantioselectivity in the [2+2+2] cycloaddition of alkenyl isocyanates with tolanes. Replacement of excess substrate with an exogenous additive affords products with consistent and higher ee’s. The increase in enantioselectivity is the result of a change in composition of a proposed rhodium(III) intermediate on the catalytic cycle. The net result is a rational probe of a short-lived rhodium(III) intermediate, and gives insight that may have applications in many rhodium catalyzed reactions. PMID:19803471

  15. Enantioselective cyclizations and cyclization cascades of samarium ketyl radicals

    Science.gov (United States)

    Kern, Nicolas; Plesniak, Mateusz P.; McDouall, Joseph J. W.; Procter, David J.

    2017-12-01

    The rapid generation of molecular complexity from simple starting materials is a key challenge in synthesis. Enantioselective radical cyclization cascades have the potential to deliver complex, densely packed, polycyclic architectures, with control of three-dimensional shape, in one step. Unfortunately, carrying out reactions with radicals in an enantiocontrolled fashion remains challenging due to their high reactivity. This is particularly the case for reactions of radicals generated using the classical reagent, SmI2. Here, we demonstrate that enantioselective SmI2-mediated radical cyclizations and cascades that exploit a simple, recyclable chiral ligand can convert symmetrical ketoesters to complex carbocyclic products bearing multiple stereocentres with high enantio- and diastereocontrol. A computational study has been used to probe the origin of the enantioselectivity. Our studies suggest that many processes that rely on SmI2 can be rendered enantioselective by the design of suitable ligands.

  16. Candida Rugosa Lipase-catalyzed Kinetic Resolution of 3-(Isobutyryloxy)methyl 4-[2-(Difluoromethoxy)phenyl]-2-methyl-5,5-dioxo-1,4-dihydrobenzothieno[3,2-b]pyridine-3-carboxylate

    NARCIS (Netherlands)

    Sobolev, A.; Zhalubovskis, R.; Franssen, M.C.R.; Vigante, B.; Chekavichus, B.; Duburs, G.; Groot, de Æ.

    2004-01-01

    The lipase-catalyzed kinetic resolution of 3-(isobutyryloxy)methyl 4-[2-(difluoromethoxy)phenyl]-2-methyl-5,5-dioxo-1,4-dihydrobenzothieno[3,2-b]pyridine-3-carboxylate has been performed. The most enantioselective reaction (E = 28) was transesterification with n-butanol in water-saturated toluene at

  17. First Novozym 435 lipase-catalyzed Morita-Baylis-Hillman reaction in the presence of amides.

    Science.gov (United States)

    Tian, Xuemei; Zhang, Suoqin; Zheng, Liangyu

    2016-03-01

    The first Novozym 435 lipase-catalyzed Morita-Baylis-Hillman (MBH) reaction with amides as co-catalyst was realized. Results showed that neither Novozym 435 nor amide can independently catalyze the reaction. This co-catalytic system that used a catalytic amount of Novozym 435 with a corresponding amount of amide was established and optimized. The MBH reaction strongly depended on the structure of aldehyde substrate, amide co-catalyst, and reaction additives. The optimized reaction yield (43.4%) was achieved in the Novozym 435-catalyzed MBH reaction of 2, 4-dinitrobenzaldehyde and cyclohexenone with isonicotinamide as co-catalyst and β-cyclodextrin as additive only in 2 days. Although enantioselectivity of Novozym 435 was not found, the results were still significant because an MBH reaction using lipase as biocatalyst was realized for the first time. Copyright © 2015 Elsevier Inc. All rights reserved.

  18. Warm hydroforming of iridium + 0.3 wt % tungsten hemishells

    International Nuclear Information System (INIS)

    Wyder, W.C.

    1976-01-01

    A technique for the production of iridium alloy hemispherical shells to be used for the primary encapsulation of plutonium-238 oxide spheres is described. The encapsulated spheres, 24 per heat source, provide the thermal heat used to drive thermoelectric converters which supply power for the Department of Defense's LES 8/9 satellites. The technique used a standard production type Hydroform machine converted for hot tooling. The iridium alloy discs were canned in stainless steel waster sheets of a larger size than the iridium discs and separated from the latter by tantalum foil barrier discs. The stainless steel was electron beam welded around the edge to form an envelope. The iridium disc assembly was heated to approximately 900 0 C and the tooling to approximately 500 0 C. After forming, the iridium shell was cut to length while in the waster sheet; and the latter was removed by dissolving in hot aqua regia. After removal of the waster sheets, the hemishells were cleaned and heat treated. Production efficiency reached a level of better than 95 percent and was maintained to produce some 600-odd hemishells

  19. Determination of traces of iridium with thiodibenzoylmethane by substoichiometric isotope dilution analysis

    International Nuclear Information System (INIS)

    Roebisch, G.; Bansse, W.; Ludwig, E.

    1980-01-01

    Iridium(III or IV) reacts with thiodibenzoylmethane on heating at pH 6 to form a 1:3 complex, which can be concentrated by extraction into chloroform. Based on this reaction, a reproducible, selective determination of iridium is achieved by means of substoichiometric isotope dilution analysis, based on 192 Ir. The linear range is 1-11 nmol of iridium. (Auth.)

  20. Evaluation of achiral templates with fluxional Brønsted basic substituents in enantioselective conjugate additions.

    Science.gov (United States)

    Adachi, Shinya; Takeda, Norihiko; Sibi, Mukund P

    2014-12-19

    Enantioselective conjugate addition of malononitrile to pyrazolidinone-derived enoates proceeds in excellent yields and high enantioselectivities. A comparison of fluxional substituents with and without a Brønsted basic site and their impact on selectivity is detailed. Molecular sieves as an additive were found to be essential to achieve high enantioselectivity.

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

    KAUST Repository

    Bucci, Alberto

    2016-06-10

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

  2. Iridium-Catalyzed Dynamic Kinetic Isomerization: Expedient Synthesis of Carbohydrates from Achmatowicz Rearrangement Products.

    Science.gov (United States)

    Wang, Hao-Yuan; Yang, Ka; Bennett, Scott R; Guo, Sheng-rong; Tang, Weiping

    2015-07-20

    A highly stereoselective dynamic kinetic isomerization of Achmatowicz rearrangement products was discovered. This new internal redox isomerization provided ready access to key intermediates for the enantio- and diastereoselective synthesis of a series of naturally occurring sugars. The nature of the de novo synthesis also enables the preparation of both enantiomers. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    KAUST Repository

    Bucci, Alberto; Menendez Rodriguez, Gabriel; Bellachioma, Gianfranco; Zuccaccia, Cristiano; Poater, Albert; Cavallo, Luigi; Macchioni, Alceo

    2016-01-01

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

  4. Iridium- and Ruthenium-Catalyzed N-alkylation of Amines with Alcohols and Amines

    DEFF Research Database (Denmark)

    Lorentz-Petersen, Linda Luise Reeh

    -helical propensity. Hereby, it was believed that more stable proteins would be obtained. Folding of the mutants was studied in terms of thermodynamics and kinetics by guanidine hydrochloride denaturation monitored by fluorescence. The results were unfortunately unreliable due to errors in the spectrofluorometer....... in the reaction, as ethyleneglycol and 1,2-ethylenediamine failed to produce piperazine. Introduction of a C-substituent on one or both of the starting materials gave Csubstituted piperazines in high yields. Synthesis of N-benzylpiperazine from ethyleneglycol and N-benzylethylenediamine was also successful. Self...... experiments were conducted and emphasized the importance of the Voigt reaction in the formation of the product. Protein folding During an external stay at The Scripps Research Institute, San Diego, California, USA, folding of the well-known protein CI2 was studied. Several mutants were synthetically prepared...

  5. Iridium‐Catalyzed Dehydrogenative Decarbonylation of Primary Alcohols with the Liberation of Syngas

    DEFF Research Database (Denmark)

    Olsen, Esben Paul Krogh; Madsen, Robert

    2012-01-01

    A new iridium‐catalyzed reaction in which molecular hydrogen and carbon monoxide are cleaved from primary alcohols in the absence of any stoichiometric additives has been developed. The dehydrogenative decarbonylation was achieved with a catalyst generated in situ from [Ir(coe)2Cl]2 (coe=cyclooct......A new iridium‐catalyzed reaction in which molecular hydrogen and carbon monoxide are cleaved from primary alcohols in the absence of any stoichiometric additives has been developed. The dehydrogenative decarbonylation was achieved with a catalyst generated in situ from [Ir(coe)2Cl]2 (coe...... to excellent yields. Ethers, esters, imides, and aryl halides are stable under the reaction conditions, whereas olefins are partially saturated. The reaction is believed to proceed by two consecutive organometallic transformations that are catalyzed by the same iridium(I)–BINAP species. First, dehydrogenation...

  6. pH sensors based on iridium oxide

    International Nuclear Information System (INIS)

    Tarlov, M.J.; Kreider, K.G.; Semancik, S.; Huang, P.

    1990-03-01

    Results are presented on the pH-potential response of dc magnetron reactively sputtered iridium oxide films. The films exhibit a nearly Nernstian response to pH, no hysteresis effects, and minimal response to ionic interferences. Sensitivity to certain redox species is observed, however. In addition, methods are discussed for preparing model iridium oxide sensor surfaces for ultrahigh vacuum surface analytical studies. Stoichiometric IrO 2 -like surfaces are shown to be relatively inert to gas phase water. However, hydroxylation of IrO 2 -like surfaces can be induced by rf water plasma treatment. 17 refs., 5 figs

  7. Welding iridium heat-source capsules for space missions

    International Nuclear Information System (INIS)

    Kanne, W.R. Jr.

    1982-03-01

    A remote computer-controlled welding station was developed to encapsulate radioactive PuO 2 in iridium. Weld quench cracking caused an interruption in production of capsules for upcoming space missions. Hot crack sensitivity of the DOP-26 iridium alloy was associated with low melting constituents in the grain boundaries. The extent of cracking was reduced but could not be eliminated by changes to the welding operation. An ultrasonic test was developed to detect underbead cracks exceeding a threshold size. Production was continued using the ultrasonic test to reject capsules with detectable cracks

  8. The role of iridium in the work-function behavior of dilute-solution tungsten, iridium alloys

    International Nuclear Information System (INIS)

    D'Cruz, L.A.

    1991-01-01

    Requirements of thermionic electrode materials have emphasized the need for substantial improvements in microstructural stability, strength and creep resistance at service temperatures in excess of 2,500K. This study utilized both chemical alloying and mechanical alloying procedures for the addition of iridium to submicron W powder followed by cold compaction and sintering. The shrinkage characteristics and microstructural development were studied in iridium-added tungsten compacts with a range of additive levels. An electron-emission study was subsequently carried out in order to evaluate the work-function behavior of the consolidated alloys. The work function was obtained from current-emission measurements from the electrode surface under UHV conditions in the temperature range of 1,800 to 2,500K using a Vacuum Emission Vehicle (VEV). The data show that the magnitude of the work function in these alloys varied with temperature and was sensitive to sub-surface iridium content

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

    Science.gov (United States)

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

    2014-12-01

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

  10. Catalyzing RE Project Development

    Energy Technology Data Exchange (ETDEWEB)

    Anderson, Kate; Elgqvist, Emma; Walker, Andy; Cutler, Dylan; Olis, Dan; DiOrio, Nick; Simpkins, Travis

    2016-09-01

    This poster details how screenings done with REopt - NREL's software modeling platform for energy systems integration and optimization - are helping to catalyze the development of hundreds of megawatts of renewable energy.

  11. Boosting Chemical Stability, Catalytic Activity, and Enantioselectivity of Metal-Organic Frameworks for Batch and Flow Reactions.

    Science.gov (United States)

    Chen, Xu; Jiang, Hong; Hou, Bang; Gong, Wei; Liu, Yan; Cui, Yong

    2017-09-27

    A key challenge in heterogeneous catalysis is the design and synthesis of heterogeneous catalysts featuring high catalytic activity, selectivity, and recyclability. Here we demonstrate that high-performance heterogeneous asymmetric catalysts can be engineered from a metal-organic framework (MOF) platform by using a ligand design strategy. Three porous chiral MOFs with the framework formula [Mn 2 L(H 2 O) 2 ] are prepared from enantiopure phosphono-carboxylate ligands of 1,1'-biphenol that are functionalized with 3,5-bis(trifluoromethyl)-, bismethyl-, and bisfluoro-phenyl substituents at the 3,3'-position. For the first time, we show that not only chemical stability but also catalytic activity and stereoselectivity of the MOFs can be tuned by modifying the ligand structures. Particularly, the MOF incorporated with -CF 3 groups on the pore walls exhibits enhanced tolerance to water, weak acid, and base compared with the MOFs with -F and -Me groups. Under both batch and flow reaction systems, the CF 3 -containing MOF demonstrated excellent reactivity, selectivity, and recyclability, affording high yields and enantioselectivities for alkylations of indoles and pyrrole with a range of ketoesters or nitroalkenes. In contrast, the corresponding homogeneous catalysts gave low enantioselectivity in catalyzing the tested reactions.

  12. Phosphine-catalyzed cycloadditions of allenic ketones: new substrates for nucleophilic catalysis.

    Science.gov (United States)

    Wallace, Debra J; Sidda, Rachel L; Reamer, Robert A

    2007-02-02

    A range of phosphine-catalyzed cycloaddition reactions of allenic ketones have been studied, extending the scope of these processes from the more widely used 2,3-butadienoates to allow access to a number of synthetically useful products. Reaction of allenyl methyl ketone 4 with exo-enones afforded spirocyclic compounds in good regioselectivity and promising enantioselectivity via a [2 + 3] cycloaddtion. Aromatic allenyl ketones undergo a phosphine-promoted dimerization to afford functionalized pyrans, leading to a formal [2 + 4] Diels-Alder product, but did not react in the [2 + 3] cycloaddition. The results from other reactions that had found utility with 2,3-butadienoates are also reported.

  13. Multigram Synthesis of a Chiral Substituted Indoline Via Copper-Catalyzed Alkene Aminooxygenation.

    Science.gov (United States)

    Sequeira, Fatima C; Bovino, Michael T; Chipre, Anthony J; Chemler, Sherry R

    2012-05-01

    (S)-5-Fluoro-2-(2,2,6,6-tetramethylpiperidin-1-yloxymethyl)-1-tosylindoline, a 2-methyleneoxy-substituted chiral indoline, was synthesized on multigram scale using an efficient copper-catalyzed enantioselective intramolecular alkene aminooxygenation. The synthesis is accomplished in four steps and the indoline is obtained in 89% ee (>98% after one recrystallization). Other highlights include efficient gram-scale synthesis of the (4R,5S)-di-Ph-box ligand and efficient separation of a monoallylaniline from its bis(allyl)aniline by-product by distillation under reduced pressure.

  14. Phosphorescent systems based on iridium(III) complexes

    NARCIS (Netherlands)

    Ulbricht, C.

    2009-01-01

    Phosphorescent iridium(III)-based complexes are experiencing a growing interest in a number of research fields. Aside from lighting and display technologies (i.e. OLEDs and LECs), they find use in various applications such as biolabeling, sensors, solar cells and water splitting. In particular, the

  15. Iridium Sulfide and Ir Promoted Mo Based Catalysts.

    Czech Academy of Sciences Publication Activity Database

    Vít, Zdeněk

    2007-01-01

    Roč. 322, - (2007), s. 142-151 ISSN 0926-860X R&D Projects: GA ČR(CZ) GA104/06/0870 Institutional research plan: CEZ:AV0Z40720504 Keywords : iridium sulfide * IrMo catalyst * hydrodesulfurization Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.166, year: 2007

  16. Prototyping iridium coated mirrors for x-ray astronomy

    Science.gov (United States)

    Döhring, Thorsten; Probst, Anne-Catherine; Stollenwerk, Manfred; Emmerich, Florian; Stehlíková, Veronika; Inneman, Adolf

    2017-05-01

    X-ray astronomy uses space-based telescopes to overcome the disturbing absorption of the Earth's atmosphere. The telescope mirrors are operating at grazing incidence angles and are coated with thin metal films of high-Z materials to get sufficient reflectivity for the high-energy radiation to be observed. In addition the optical payload needs to be light-weighted for launcher mass constrains. Within the project JEUMICO, an acronym for "Joint European Mirror Competence", the Aschaffenburg University of Applied Sciences and the Czech Technical University in Prague started a collaboration to develop mirrors for X-ray telescopes. The X-ray telescopes currently developed within this Bavarian- Czech project are of Lobster eye type optical design. Corresponding mirror segments use substrates of flat silicon wafers which are coated with thin iridium films, as this material is promising high reflectivity in the X-ray range of interest. The deposition of the iridium films is based on a magnetron sputtering process. Sputtering with different parameters, especially by variation of the argon gas pressure, leads to iridium films with different properties. In addition to investigations of the uncoated mirror substrates the achieved surface roughness has been studied. Occasional delamination of the iridium films due to high stress levels is prevented by chromium sublayers. Thereby the sputtering parameters are optimized in the context of the expected reflectivity of the coated X-ray mirrors. In near future measurements of the assembled mirror modules optical performances are planned at an X-ray test facility.

  17. The Iridium (tm) system: Personal communications anytime, anyplace

    Science.gov (United States)

    Hatlelid, John E.; Casey, Larry

    1993-01-01

    The Iridium system is designed to provide handheld personal communications between diverse locations around the world at any time and without prior knowledge of the location of the personal units. This paper provides an overview of the system, the services it provides, its operation, and an overview of the commercial practices and relatively high volume satellite production techniques which will make the system cost effective. A constellation of 66 satellites will provide an orbiting, spherical-shell, infrastructure for this global calling capability. The satellites act as tall cellular towers and allow convenient operation for portable handheld telephones. The system will provide a full range of services including voice, paging, data, geolocation, and fax capabilities. Motorola is a world leader in the production of high volume, high quality, reliable telecommunications hardware. One of Iridium's goals is to apply these production techniques to high reliability space hardware. Concurrent engineering, high performance work teams, advanced manufacturing technologies, and improved assembly and test methods are some of the techniques that will keep the Iridium system cost effective. Mobile, global, flexible personal communications are coming that will allow anyone to call or receive a call from/to anyplace at anytime. The Iridium system will provide communications where none exist today. This connectivity will allow increased information transfer, open new markets for various business endeavors, and in general increase productivity and development.

  18. Dose determination in breast tumor in brachytherapy using Iridium-192

    International Nuclear Information System (INIS)

    Okuno, S.F.

    1984-01-01

    Thermoluminescent dosimetry studies in vivo and in vitro aiming to determing radiation dose in the breast tumor, in brachytherapy using Iridium-192 was done. The correlation between radiation doses in tumor and external surface of the breast was investigated for correcting the time interval of radiation source implantation. (author) [pt

  19. Regio- and Enantioselective Sequential Dehalogenation of rac-1,3-Dibromobutane by Haloalkane Dehalogenase LinB.

    Science.gov (United States)

    Gross, Johannes; Prokop, Zbyněk; Janssen, Dick; Faber, Kurt; Hall, Mélanie

    2016-08-03

    The hydrolytic dehalogenation of rac-1,3-dibromobutane catalyzed by the haloalkane dehalogenase LinB from Sphingobium japonicum UT26 proceeds in a sequential fashion: initial formation of intermediate haloalcohols followed by a second hydrolytic step to produce the final diol. Detailed investigation of the course of the reaction revealed favored nucleophilic displacement of the sec-halogen in the first hydrolytic event with pronounced R enantioselectivity. The second hydrolysis step proceeded with a regioselectivity switch at the primary position, with preference for the S enantiomer. Because of complex competition between all eight possible reactions, intermediate haloalcohols formed with moderate to good ee ((S)-4-bromobutan-2-ol: up to 87 %). Similarly, (S)-butane-1,3-diol was formed at a maximum ee of 35 % before full hydrolysis furnished the racemic diol product. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Role of keto–enol tautomerization in a chiral phosphoric acid catalyzed asymmetric thiocarboxylysis of meso-epoxide: a DFT study

    KAUST Repository

    Ajitha, Manjaly John; Huang, Kuo-Wei

    2015-01-01

    The mechanism of a chiral phosphoric acid catalyzed thiocarboxylysis of meso-epoxide was investigated by density functional theory (DFT) calculations (M06-2X). The nucleophilic ring opening of epoxide by thiobenzoic acid was found to proceed via a concerted termolecular transition state with a simultaneous dual proton transfer to yield the β-hydroxy thioester product. Electrostatic interactions together with the steric environment inside the chiral catalyst play an important role in determining the enantioselectivity of the reaction.

  1. Catalytic Asymmetric Piancatelli Rearrangement: Brønsted Acid Catalyzed 4π Electrocyclization for the Synthesis of Multisubstituted Cyclopentenones

    KAUST Repository

    Cai, Yunfei

    2016-10-13

    The first catalytic asymmetric Piancatelli reaction is reported. Catalyzed by a chiral Brønsted acid, the rearrangement of a wide range of furylcarbinols with a series of aniline derivatives provides valuable aminocyclopentenones in high yields as well as excellent enantioselectivities and diastereoselectivities. The high value of the aza-Piancatelli rearrangement was demonstrated by the synthesis of a cyclopentane-based hNK1 antagonist analogue.

  2. Role of keto–enol tautomerization in a chiral phosphoric acid catalyzed asymmetric thiocarboxylysis of meso-epoxide: a DFT study

    KAUST Repository

    Ajitha, Manjaly John

    2015-09-15

    The mechanism of a chiral phosphoric acid catalyzed thiocarboxylysis of meso-epoxide was investigated by density functional theory (DFT) calculations (M06-2X). The nucleophilic ring opening of epoxide by thiobenzoic acid was found to proceed via a concerted termolecular transition state with a simultaneous dual proton transfer to yield the β-hydroxy thioester product. Electrostatic interactions together with the steric environment inside the chiral catalyst play an important role in determining the enantioselectivity of the reaction.

  3. Insight into the stereospecificity of short-chain thermus thermophilus alcohol dehydrogenase showing pro-S hydride transfer and prelog enantioselectivity.

    Science.gov (United States)

    Pennacchio, Angela; Giordano, Assunta; Esposito, Luciana; Langella, Emma; Rossi, Mosè; Raia, Carlo A

    2010-04-01

    The stereochemistry of the hydride transfer in reactions catalyzed by NAD(H)-dependent alcohol dehydrogenase from Thermus thermophilus HB27 was determined by means of (1)H-NMR spectroscopy. The enzyme transfers the pro-S hydrogen of [4R-(2)H]NADH and exhibits Prelog specificity. Enzyme-substrate docking calculations provided structural details about the enantioselectivity of this thermophilic enzyme. These results give additional insights into the diverse active site architectures of the largely versatile short-chain dehydrogenase superfamily enzymes. A feasible protocol for the synthesis of [4R-(2)H]NADH with high yield was also set up by enzymatic oxidation of 2-propanol-d(8) catalyzed by Bacillus stearothermophilus alcohol dehydrogenase.

  4. Single Pot Selective Hydrogenation of Furfural to 2-Methylfuran Over Carbon Supported Iridium Catalysts

    KAUST Repository

    Date, Nandan S; Hengne, Amol Mahalingappa; Huang, Kuo-Wei; Chikate, Rajeev C.; Rode, C. V.

    2018-01-01

    Various iridium supported carbon catalysts were prepared and screened for direct hydrogenation of furfural (FFR) to 2-methyl furan (2-MF). Amongest these, 5% Ir/C showed excellent results with complete FFR conversion and highest selectivity of 95% to 2-MF at very low H2 pressure of 100 psig. Metallic (Iro) and oxide ( IrO2) phases of Ir catalyzed first step hydrogenation involving FFR to FAL and subsequent hydrogenation to 2-MF,respecively. This was confirmed by XPS analysis and some controlled experiments. At low temperature of 140 oC, almost equal selectivities of FAL (42%) and 2-MF (43%) were observed, while higher temperature (220oC) favored selective hydrodeoxygenation. At optimized temperature, 2-MF formed selectively while higher pressure and higher catalyst loading favored ring hydrogenation of furfural rather than side chain hydrogenation. With combination of several control experimental results and detailed catalyst characterization, a plausible reaction pathway has been proposed for selective formation of 2-MF. The selectivity to various other products in FFR hydrogenation can be manipulated by tailoring the reaction conditions over the same catalyst.

  5. Single Pot Selective Hydrogenation of Furfural to 2-Methylfuran Over Carbon Supported Iridium Catalysts

    KAUST Repository

    Date, Nandan S

    2018-03-20

    Various iridium supported carbon catalysts were prepared and screened for direct hydrogenation of furfural (FFR) to 2-methyl furan (2-MF). Amongest these, 5% Ir/C showed excellent results with complete FFR conversion and highest selectivity of 95% to 2-MF at very low H2 pressure of 100 psig. Metallic (Iro) and oxide ( IrO2) phases of Ir catalyzed first step hydrogenation involving FFR to FAL and subsequent hydrogenation to 2-MF,respecively. This was confirmed by XPS analysis and some controlled experiments. At low temperature of 140 oC, almost equal selectivities of FAL (42%) and 2-MF (43%) were observed, while higher temperature (220oC) favored selective hydrodeoxygenation. At optimized temperature, 2-MF formed selectively while higher pressure and higher catalyst loading favored ring hydrogenation of furfural rather than side chain hydrogenation. With combination of several control experimental results and detailed catalyst characterization, a plausible reaction pathway has been proposed for selective formation of 2-MF. The selectivity to various other products in FFR hydrogenation can be manipulated by tailoring the reaction conditions over the same catalyst.

  6. Pyrones to pyrans: enantioselective radical additions to acyloxy pyrones.

    Science.gov (United States)

    Sibi, Mukund P; Zimmerman, Jake

    2006-10-18

    This paper describes a highly site-, diastereo-, and enantioselective intermolecular radical addition/hydrogen atom transfer to hydroxypyrone pyromeconic and kojic acids. The methodology can be extended to the formation of chiral quaternary centers. The products obtained are densely functionalized pyran moieties. The products contain structural features amenable for the introduction of additional substituents.

  7. Lanthanide Lewis acid-mediated enantioselective conjugate radical additions.

    Science.gov (United States)

    Sibi, Mukund P; Manyem, Shankar

    2002-08-22

    [reaction: see text] Lanthanide triflates along with proline-derived ligands have been found to be efficient catalysts for enantioselective conjugate addition of nucleophilic radicals to enoates. N-Acyl oxazolidinones, when used as achiral additives, gave meaningful enhancements in the ees for the product.

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

    KAUST Repository

    Millet, Anthony; Lefebvre, Quentin; Rueping, Magnus

    2016-01-01

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

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

    KAUST Repository

    Millet, Anthony

    2016-06-20

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

  10. Graphene-based hybrid for enantioselective sensing applications.

    Science.gov (United States)

    Zor, Erhan; Morales-Narváez, Eden; Alpaydin, Sabri; Bingol, Haluk; Ersoz, Mustafa; Merkoçi, Arben

    2017-01-15

    Chirality is a major field of research of chemical biology and is essential in pharmacology. Accordingly, approaches for distinguishing between different chiral forms of a compound are of great interest. We report on an efficient and generic enantioselective sensor that is achieved by coupling reduced graphene oxide with γ-cyclodextrin (rGO/γ-CD). The enantioselective sensing capability of the resulting structure was operated in both electrical and optical mode for of tryptophan enantiomers (D-/L-Trp). In this sense, voltammetric and photoluminescence measurements were conducted and the experimental results were compared to molecular docking method. We gain insight into the occurring recognition mechanism with selectivity toward D- and L-Trp as shown in voltammetric, photoluminescence and molecular docking responses. As an enantioselective solid phase on an electrochemical transducer, thanks to the different dimensional interaction of enantiomers with hybrid material, a discrepancy occurs in the Gibbs free energy leading to a difference in oxidation peak potential as observed in electrochemical measurements. The optical sensing principle is based on the energy transfer phenomenon that occurs between photoexcited D-/L-Trp enantiomers and rGO/γ-CD giving rise to an enantioselective photoluminescence quenching due to the tendency of chiral enantiomers to form complexes with γ-CD in different molecular orientations as demonstrated by molecular docking studies. The approach, which is the first demonstration of applicability of molecular docking to show both enantioselective electrochemical and photoluminescence quenching capabilities of a graphene-related hybrid material, is truly new and may have broad interest in combination of experimental and computational methods for enantiosensing of chiral molecules. Copyright © 2016 Elsevier B.V. All rights reserved.

  11. Mechanistic studies of copper(I)-catalyzed 1,3-halogen migration.

    Science.gov (United States)

    Van Hoveln, Ryan; Hudson, Brandi M; Wedler, Henry B; Bates, Desiree M; Le Gros, Gabriel; Tantillo, Dean J; Schomaker, Jennifer M

    2015-04-29

    An ongoing challenge in modern catalysis is to identify and understand new modes of reactivity promoted by earth-abundant and inexpensive first-row transition metals. Herein, we report a mechanistic study of an unusual copper(I)-catalyzed 1,3-migration of 2-bromostyrenes that reincorporates the bromine activating group into the final product with concomitant borylation of the aryl halide bond. A combination of experimental and computational studies indicated this reaction does not involve any oxidation state changes at copper; rather, migration occurs through a series of formal sigmatropic shifts. Insight provided from these studies will be used to expand the utility of aryl copper species in synthesis and develop new ligands for enantioselective copper-catalyzed halogenation.

  12. Large-scale ruthenium- and enzyme-catalyzed dynamic kinetic resolution of (rac-1-phenylethanol

    Directory of Open Access Journals (Sweden)

    Bäckvall Jan-E

    2007-12-01

    Full Text Available Abstract The scale-up of the ruthenium- and enzyme-catalyzed dynamic kinetic resolution (DKR of (rac-1-phenylethanol (2 is addressed. The immobilized lipase Candida antarctica lipase B (CALB was employed for the resolution, which shows high enantioselectivity in the transesterification. The ruthenium catalyst used, (η 5-C5Ph5RuCl(CO2 1, was shown to possess very high reactivity in the "in situ" redox racemization of 1-phenylethanol (2 in the presence of the immobilized enzyme, and could be used in 0.05 mol% with high efficiency. Commercially available isopropenyl acetate was employed as acylating agent in the lipase-catalyzed transesterifications, which makes the purification of the product very easy. In a successful large-scale DKR of 2, with 0.05 mol% of 1, (R-1-phenylethanol acetate (3 was obtained in 159 g (97% yield in excellent enantiomeric excess (99.8% ee.

  13. Screening the collision risk of the Iridium 33 - Cosmos 2251 Clouds

    OpenAIRE

    Rossi, Alessandro; Valsecchi, Giovanni Battista

    2011-01-01

    More than 10 years ago, in Rossi, Valsecchi and Farinella (Nature, 1999), it was shown how a near polar multi-plane constellation such as Iridium is particularly at risk of a collisional cascade if one of its satellites is first accidentally fragmented. Those results are recalled and actualized in the light of the real collision of February 2009, between Iridium 33 and Cosmos 2251. The collision risk, for the remaining Iridium satellites, arising from the two clouds of fragments generated by ...

  14. Organocatalysts for enantioselective synthesis of fine chemicals: definitions, trends and developments

    Directory of Open Access Journals (Sweden)

    Chiara Palumbo

    2015-02-01

    Full Text Available Organocatalysis, that is the use of small organic molecules to catalyze organic transformations, has been included among the most successful concepts in asymmetric catalysis, and it has been used for the enantioselective construction of C–C, C–N, C–O, C–S, C–P and C–halide bonds. Since the seminal works in early 2000, the scientific community has been paying an ever-growing attention to the use of organocatalysts for the synthesis, with high yields and remarkable stereoselectivities, of optically active fine chemicals of interest for the pharmaceutical industry. A brief overview is here presented about the two main classes of substrate activation by the catalyst: covalent organocatalysis and non-covalent organocatalysis, with a more stringent focus on some recent outcomes in the field of the latter and of hydrogen bond-based catalysis. Finally, some successful examples of heterogenization of organocatalysts are also discussed, in the view of a potential industrial exploitation.

  15. A projector of iridium 192 wires: motivations and preliminary studies

    International Nuclear Information System (INIS)

    Cosset, J.M.; Gerbaulet, A.; Chassagne, D.

    1979-01-01

    Though the majority of procedures involved in curietherapy with Iridium 192 wires cause very few problems concerning radiation protection, this is not true in all cases: in elderly of debilitated patients, young children, or when using special techniques (curietherapy for prostate of bladder cancers for example). In these cases, the need for frequent treatment exposes the therapists to increased doses. The projector of Iridium 192 wires was conceived in order to reduce this irradiated hazard. A simple manipulation places the radioactive wires in a lead container during treatment, and then replaces them in the right position after therapy. This apparatus appears to offer the possibility of: an almost total protection of the therapists, and thus an opportunity for enlarging the indications for curietherapy; an improved quality of treatment to the patient during the application [fr

  16. Network flexibility of the IRIDIUM (R) Global Mobile Satellite System

    Science.gov (United States)

    Hutcheson, Jonathan; Laurin, Mala

    1995-01-01

    The IRIDIUM system is a global personal communications system supported by a constellation of 66 low earth orbit (LEO) satellites and a collection of earth-based 'gateway' switching installations. Like traditional wireless cellular systems, coverage is achieved by a grid of cells in which bandwidth is reused for spectral efficiency. Unlike any cellular system ever built, the moving cells can be shared by multiple switching facilities. Noteworthy features of the IRIDIUM system include inter-satellite links, a GSM-based telephony architecture, and a geographically controlled system access process. These features, working in concert, permit flexible and reliable administration of the worldwide service area by gateway operators. This paper will explore this unique concept.

  17. Rhodium Catalyzed Decarbonylation

    DEFF Research Database (Denmark)

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

    2017-01-01

    Rhodium catalyzed decarbonylation has developed significantly over the last 50 years and resulted in a wide range of reported catalyst systems and reaction protocols. Besides experimental data, literature also includes mechanistic studies incorporating Hammett methods, analysis of kinetic isotope...

  18. Diphosphinoazine Rhodium(I) and Iridium(I) Complexes

    Czech Academy of Sciences Publication Activity Database

    Pošta, Martin; Čermák, Jan; Vojtíšek, P.; Císařová, I.

    2006-01-01

    Roč. 71, č. 2 (2006), s. 197-206 ISSN 0010-0765 R&D Projects: GA ČR(CZ) GA203/01/0554; GA ČR(CZ) GA203/99/M037 Institutional research plan: CEZ:AV0Z40720504 Keywords : diphosphinoazines * rhodium complexes * iridium complexes Subject RIV: CC - Organic Chemistry Impact factor: 0.881, year: 2006

  19. Synthesis, structure, redox and spectra of green iridium complexes ...

    Indian Academy of Sciences (India)

    Reactions of IrCl3 ⋅ H2O with the ligands, 2-[(phenylamino)phenylazo]pyridine (HL1a) and 2-[(-tolylamino)phenylazo]pyridine (HL1b) produce [Ir(L1)2]Cl (L1 = L1a, [1]Cl and L1 = L1b, [2]Cl) along with many unidentified products. The iridium complexes have been characterized by various techniques such as X-ray ...

  20. Ligand-Controlled Synthesis of Azoles via Ir-Catalyzed Reactions of Sulfoxonium Ylides with 2-Amino Heterocycles.

    Science.gov (United States)

    Phelps, Alicia M; Chan, Vincent S; Napolitano, José G; Krabbe, Scott W; Schomaker, Jennifer M; Shekhar, Shashank

    2016-05-20

    An iridium-catalyzed method was developed for the synthesis of imidazo-fused pyrrolopyrazines. The presence or absence of a nitrogenated ligand controlled the outcome of the reaction, leading to simple β-keto amine products in the absence of added ligand and the cyclized 7- and 8-substituted-imidazo[1,2-a]pyrrolo[2,3-e]pyrazine products in the presence of ligand. This catalyst control was conserved across a variety of ylide and amine coupling partners. The substrate was shown to act as a ligand for the iridium catalyst in the absence of other ligands via NMR spectroscopy. Kinetic studies indicated that formation of the Ir-carbene was reversible and the slow step of the reaction. These mechanistic investigations suggest that the β-keto amine products form via an intramolecular carbene N-H insertion, and the imidazopyrrolopyrazines form via an intermolecular carbene N-H insertion.

  1. The rabbit liver microsomal biotransformation of 1,1-dialkylethylenes: enantioface selection of epoxidation and enantioselectivity of epoxide hydrolysis.

    Science.gov (United States)

    Bellucci, G; Chiappe, C; Cordoni, A; Marioni, F

    1994-01-01

    The rabbit liver microsomal biotransformation of alpha-methylstyrene (1a), 2-methyl-1-hexene (1b), 2,4,4-trimethyl-1-pentene (1c), and 1,3,3-trimethyl-1-butene (1d) has been investigated with the aim at establishing the enantioface selection of the cytochrome P-450-promoted epoxidation of the double bond and the enantioselectivity of microsomal epoxide hydrolase(mEH)-catalyzed hydrolysis of the resulting epoxides. GLC on a Chiraldex G-TA (ASTEC) column was used to determine the enantiomeric composition of the products. The epoxides 2 first produced in incubations carried out in the presence of an NADPH regenerating system were not detected, being rapidly hydrolyzed by mEH to diols 3. The enantiomeric composition of the latter showed that no enantioface selection occurred in the epoxidation of 1c and 1d, and a very low (8%) ee of the (R)-epoxide was formed from 1b. Incubation of racemic epoxides 2b-d with the microsomal fraction showed that the mEH-catalyzed hydrolysis of 2c and 2d was practically nonenantioselective, while that of 2b exhibited a selectivity E = 4.9 favoring the hydrolysis of the (S)-enantiomer. A comparison of these results with those previously obtained for linear and branched chain alkyl monosubstituted oxiranes shows that the introduction of the second alkyl substituent suppresses the selectivity of the mEH reaction of the latter and reverses that of the former substrates.

  2. Enantioselective Epoxide Polymerization Using a Bimetallic Cobalt Catalyst

    KAUST Repository

    Thomas, Renee M.

    2010-11-24

    A highly active enantiopure bimetallic cobalt complex was explored for the enantioselective polymerization of a variety of monosubstituted epoxides. The polymerizations were optimized for high rates and stereoselectivity, with s-factors (kfast/kslow) for most epoxides exceeding 50 and some exceeding 300, well above the threshold for preparative utility of enantiopure epoxides and isotactic polyethers. Values for mm triads of the resulting polymers are typically greater than 95%, with some even surpassing 98%. In addition, the use of a racemic catalyst allowed the preparation of isotactic polyethers in quantitative yields. The thermal properties of these isotactic polyethers are presented, with many polymers exhibiting high T m values. This is the first report of the rapid synthesis of a broad range of highly isotactic polyethers via the enantioselective polymerization of racemic epoxides. © 2010 American Chemical Society.

  3. Enantioselective Epoxide Polymerization Using a Bimetallic Cobalt Catalyst

    KAUST Repository

    Thomas, Renee M.; Widger, Peter C. B.; Ahmed, Syud M.; Jeske, Ryan C.; Hirahata, Wataru; Lobkovsky, Emil B.; Coates, Geoffrey W.

    2010-01-01

    A highly active enantiopure bimetallic cobalt complex was explored for the enantioselective polymerization of a variety of monosubstituted epoxides. The polymerizations were optimized for high rates and stereoselectivity, with s-factors (kfast/kslow) for most epoxides exceeding 50 and some exceeding 300, well above the threshold for preparative utility of enantiopure epoxides and isotactic polyethers. Values for mm triads of the resulting polymers are typically greater than 95%, with some even surpassing 98%. In addition, the use of a racemic catalyst allowed the preparation of isotactic polyethers in quantitative yields. The thermal properties of these isotactic polyethers are presented, with many polymers exhibiting high T m values. This is the first report of the rapid synthesis of a broad range of highly isotactic polyethers via the enantioselective polymerization of racemic epoxides. © 2010 American Chemical Society.

  4. Enhancing the potential of enantioselective organocatalysis with light

    Science.gov (United States)

    Silvi, Mattia; Melchiorre, Paolo

    2018-02-01

    Organocatalysis—catalysis mediated by small chiral organic molecules—is a powerful technology for enantioselective synthesis, and has extensive applications in traditional ionic, two-electron-pair reactivity domains. Recently, organocatalysis has been successfully combined with photochemical reactivity to unlock previously inaccessible reaction pathways, thereby creating new synthetic opportunities. Here we describe the historical context, scientific reasoning and landmark discoveries that were essential in expanding the functions of organocatalysis to include one-electron-mediated chemistry and excited-state reactivity.

  5. Enantioselective synthesis of alpha,beta-disubstituted-beta-amino acids.

    Science.gov (United States)

    Sibi, Mukund P; Prabagaran, Narayanasamy; Ghorpade, Sandeep G; Jasperse, Craig P

    2003-10-01

    Highly diastereoselective and enantioselective addition of N-benzylhydroxylamine to imides 17 and 20-30 produces alpha,beta-trans-disubstituted N-benzylisoxazolidinones 19 and 31-41. These reactions proceed in 60-96% ee with 93-99% de's using 5 mol % of Mg(NTf2)2 and ligand 18. The product isoxazolidinones can be hydrogenolyzed directly to provide alpha,beta-disubstituted-beta-amino acids.

  6. Enantioselective conjugate radical addition to alpha'-hydroxy enones.

    Science.gov (United States)

    Lee, Sunggi; Lim, Chae Jo; Kim, Sunggak; Subramaniam, Rajesh; Zimmerman, Jake; Sibi, Mukund P

    2006-09-14

    Enantioselective conjugate radical addition to alpha'-hydroxy alpha,beta-unsaturated ketones, compounds containing bidentate donors, has been investigated. It has been found that radical additions to alpha'-hydroxy alpha,beta-unsaturated ketones in the presence of Mg(NTf2)2 and bisoxazoline ligand 5a proceeded cleanly, yielding the addition products in high chemical yields and good enantiomeric excesses.

  7. Catalytic enantioselective alkene aminohalogenation/cyclization involving atom transfer.

    Science.gov (United States)

    Bovino, Michael T; Chemler, Sherry R

    2012-04-16

    Problem solved: the title reaction was used for the synthesis of chiral 2-bromo, chloro, and iodomethyl indolines and 2-iodomethyl pyrrolidines. Stereocenter formation is believed to occur by enantioselective cis aminocupration and C-X bond formation is believed to occur by atom transfer. The ultility of the products as versatile synthetic intermediates was demonstrated, as was a radical cascade cyclization sequence. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. The use of phosphite-type ligands in the Ir-catalyzed asymmetric hydrogenation of heterocyclic compounds.

    Science.gov (United States)

    Lyubimov, Sergey E; Ozolin, Dmitry V; Ivanov, Pavel Yu; Melman, Artem; Velezheva, Valeriya S; Davankov, Vadim A

    2014-01-01

    A series of chiral phosphite-type ligands was tested in asymmetric Ir-catalyzed hydrogenation of quinolines and 2,4,5,6-tetrahydro-1H-pyrazino(3,2,1-j,k)carbazole. Hydrogenation of quinaldine hydrochloride provided superior enantioselectivity up to 65% ee compared to quinaldine free base. The ligands were tested for the first time in the asymmetric Ir-Ircatalyzed hydrogenation of 2,4,5,6-tetrahydro-1H-pyrazino(3,2,1-j,k)carbazole yielding the antidepressant drug, pirlindole. © 2013 Wiley Periodicals, Inc.

  9. γ-Sultam-cored N,N-ligands in the ruthenium(ii)-catalyzed asymmetric transfer hydrogenation of aryl ketones.

    Science.gov (United States)

    Rast, Slavko; Modec, Barbara; Stephan, Michel; Mohar, Barbara

    2016-02-14

    The synthesis of new enantiopure syn- and anti-3-(α-aminobenzyl)-benzo-γ-sultam ligands 6 and their application in the ruthenium(ii)-catalyzed asymmetric transfer hydrogenation (ATH) of ketones using formic acid/triethylamine is described. In particular, benzo-fused cyclic ketones afforded excellent enantioselectivities in reasonable time employing a low loading of the syn ligand-containing catalyst. A never-before-seen dynamic kinetic resolution (DKR) during reduction of a γ-keto carboxylic ester (S7) derivative of 1-indanone is realized leading as well to excellent induction.

  10. Rhodium-catalyzed Asymmetric Hydrogenation of α-Dehydroamino Ketones: A General Approach to Chiral α-amino Ketones.

    Science.gov (United States)

    Gao, Wenchao; Wang, Qingli; Xie, Yun; Lv, Hui; Zhang, Xumu

    2016-01-01

    Rhodium/DuanPhos-catalyzed asymmetric hydrogenation of aliphatic α-dehydroamino ketones has been achieved and afforded chiral α-amino ketones in high yields and excellent enantioselectives (up to 99 % ee), which could be reduced further to chiral β-amino alcohols by LiAlH(tBuO)3 with good yields. This protocol provides a readily accessible route for the synthesis of chiral α-amino ketones and chiral β-amino alcohols. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. An N-Linked Bidentate Phosphoramidite Ligand (N-Me-BIPAM for Rhodium-Catalyzed Asymmetric 1,4-Addition of Arylboronic Acids to α,β-Unsaturated Ketones

    Directory of Open Access Journals (Sweden)

    Norio Miyaura

    2012-12-01

    Full Text Available A new bidentate phosphoramidite (N-Me-BIPAM based on Shibasaki’s N-linked BINOL was synthesized. This ligand appears to be highly effective for rhodium-catalyzed asymmetric conjugated addition of arylboronic acids to α,β-unsaturated enones. The reaction of ortho-substituted arylboronic acid with acyclic and cyclic enones provides the corresponding products in good yields and enantioselectivities.

  12. In vitro enantioselective human liver microsomal metabolism and prediction of in vivo pharmacokinetic parameters of tetrabenazine by DLLME-CE.

    Science.gov (United States)

    Bocato, Mariana Zuccherato; de Lima Moreira, Fernanda; de Albuquerque, Nayara Cristina Perez; de Gaitani, Cristiane Masetto; de Oliveira, Anderson Rodrigo Moraes

    2016-09-05

    A new capillary electrophoresis method for the enantioselective analysis of cis- and trans- dihydrotetrabenazine (diHTBZ) after in vitro metabolism by human liver microsomes (HLMs) was developed. The chiral electrophoretic separations were performed by using tris-phosphate buffer (pH 2.5) containing 1% (w/v) carboxymethyl-β-CD as background electrolyte with an applied voltage of +15kV and capillary temperature kept at 15°C. Dispersive liquid-liquid microextraction was employed to extract the analytes from HLMs. Dichloromethane was used as extraction solvent (75μL) and acetone as disperser solvent (150μL). The method was validated according to official guidelines and showed to be linear over the concentration range of 0.29-19.57μmolL(-1) (r=0.9955) for each metabolite enantiomer. Within- and between-day precision and accuracy evaluated by relative standard deviation and relative error were lower than 15% for all enantiomers. The stability assay showed that the analytes kept stable under handling, storage and in metabolism conditions. After method validation, an enantioselective in vitro metabolism and in vivo pharmacokinetic prediction was carried out. This study showed a stereoselective metabolism and the observed kinetic profile indicated a substrate inhibition behavior. DiHTBZ enantiomers were catalyzed mainly by CYP2C19 and the predicted clearance suggests that liver metabolism is the main route for TBZ elimination which supports the literature data. Copyright © 2016 Elsevier B.V. All rights reserved.

  13. Iridium: Global OTH data communications for high altitude scientific ballooning

    Science.gov (United States)

    Denney, A.

    beneficial points provided by the Iridium platform include pure global accessibility (as well as polar), cost effectiveness because it is available as a COTS (Commercially Off The Shelf) technology, reliability in that the equipment must operate in extreme conditions (near space), integration and development time into current systems must be minimized. As a bonus Motorola and NAL Research Corporation are developing SBD (Short Burst Data) into the Iridium network. This may lead the way to a global IP (Internet Protocol) node based ballooning platform. The Iridium satellite data modems employ the Iridium Low-Earth Orbit (LEO) satellite network. The scope of this paper is to introduce an OTH communications alternative, albeit not necessarily a primary one, to existing ballooning platforms using COTS based emerging technologies. Design aspects, characteristics, actual flight testing statistics, principles of the Iridium modems and communication paths are described including payload and support instrumentation interfacing. Not limited to high altitude ballooning, the Iridium communications platform opens a new era in remote commanding and data retrieval.

  14. Enantioselective N-demethylation and hydroxylation of sibutramine in human liver microsomes and recombinant cytochrome p-450 isoforms.

    Science.gov (United States)

    Shinde, Dhananjay D; Kim, Min-Jung; Jeong, Eun-Sook; Kim, Yang-Weon; Lee, Ji-Woo; Shin, Jae-Gook; Kim, Dong-Hyun

    2014-01-01

    The enantioselective metabolism of sibutramine was examined using human liver microsomes (HLM) and recombinant cytochrome P-450 (CYP) isoforms. This drug is metabolized to N-mono-desmethyl- (M1) and N,N-di-desmethylsibutramine (M2), and subsequent hydroxylation results in hydroxyl M1 (HM1) and hydroxyl M2 (HM2). No significant difference was noted in formation of M1from sibutramine between R- and S-sibutramine in HLM. However, S-enantiomers of M1 and M2 were preferentially metabolized to M2, HM1, and HM2compared to R-enantiomers in HLM, and intrinsic clearance (Clint) ratios of S-enantiomers/R-enantiomers were 1.97, 4.83, and 9.94 for M2, HM1, and HM2, respectively. CYP3A4 and CYP3A5 were only involved in the formation of M1, whereas CYP2B6 and CYP2C19 were responsible for all metabolic reactions of sibutramine. CYP2C19 and CYP3A5 displayed catalytic preference for S-sibutramine to S-M1, whereas CYP2B6 and CYP3A4 showed little or no stereoselectivity in metabolism of sibutramine to M1. In the case of M2 formation, CYP2B6 metabolized S-M1 more rapidly than R-M1 with a Clint ratio of 2.14. However, CYP2C19 catalyzed less S-M1 than R-M1 and the Clint ratio of S-M1 to R-M1 was 0.65. The most significant enantioselectivity was observed in formation of HM1 from M1, and HM2 from M2. CYP2B6 and CYP2C19 exhibited preferential catalysis of formation of hydroxyl metabolites from S-enantiomers rather than R-enantiomers. These results indicate that S-sibutramine was more rapidly metabolized by CYP isoforms than R-sibutramine, and that enantioselective metabolism needs to be considered in drug interactions involving sibutramine and co-administered drugs.

  15. Enantioselective carbenoid insertion into C(sp3–H bonds

    Directory of Open Access Journals (Sweden)

    J. V. Santiago

    2016-05-01

    Full Text Available The enantioselective carbenoid insertion into C(sp3–H bonds is an important tool for the synthesis of complex molecules due to the high control of enantioselectivity in the formation of stereogenic centers. This paper presents a brief review of the early issues, related mechanistic studies and recent applications on this chemistry area.

  16. Application of enantioselective radical reactions: synthesis of (+)-ricciocarpins A and B.

    Science.gov (United States)

    Sibi, Mukund P; He, Liwen

    2004-05-27

    Enantioselective synthesis of (+)-ricciocarpins A and B has been achieved in 41 and 45% overall yields, respectively, starting from a beta-substituted oxazolidinone. The key steps in the strategy are an enantioselective conjugate radical addition and the addition of a furyl organometallic to a key aldehyde intermediate. [reaction--see text

  17. Enantioselective H-atom transfer reaction: a strategy to synthesize formaldehyde aldol products.

    Science.gov (United States)

    Sibi, Mukund P; Patil, Kalyani

    2005-04-14

    [reaction: see text] Enantioselective radical alkylation of Baylis-Hillman adducts furnished aldol products in good yield and selectivity. The results illustrate that the selectivity in the hydrogen atom transfer is dependent on the size of the ester substituent, with smaller substituents providing better enantioselectivity.

  18. Reverse saturable absorption (RSA) in fluorinated iridium derivatives

    Science.gov (United States)

    Ferry, Michael J.; O'Donnell, Ryan M.; Bambha, Neal; Ensley, Trenton R.; Shensky, William M.; Shi, Jianmin

    2017-08-01

    The photophysical properties of cyclometallated iridium compounds are beneficial for nonlinear optical (NLO) applications, such as the design of reverse saturable absorption (RSA) materials. We report on the NLO characterization of a family of compounds of the form [Ir(pbt)2(LX)], where pbt is 2-phenylbenzothiazole and LX is a beta-diketonate ligand. In particular, we investigate the effects of trifluoromethylation on compound solubility and photophysics compared to the parent acetylacetonate (acac) version. The NLO properties, such as the singlet and triplet excited-state cross sections, of these compounds were measured using the Z-scan technique. The excited-state lifetimes were determined from visible transient absorption spectroscopy.

  19. Angular absorption of iridium - ICW12 needles: practical considerations

    International Nuclear Information System (INIS)

    Szymczyk, W.; Lesiak, J.

    1984-01-01

    An analysis was made of two potential sources of error in Ir 192 dosimetry: the effect of angular absorption and the differences in the ionization constants found in literature. Corrections for selfabsorption in the ICW12 iridium source were determined from measurements and calculations. It was found that the decrease in the dose caused by the angular absorption in the central therapeutic area of a typical implantation can exceed 5 percent. The need for employing the concept of ''constant exposure rate'' is stressed as well as that for using angular absorption in the form of absorption. 13 refs., 6 figs., 1 tab. (author)

  20. N,N'-dioxide/nickel(II)-catalyzed asymmetric inverse-electron-demand hetero-diels-alder reaction of β,γ-unsaturated α-ketoesters with enecarbamates.

    Science.gov (United States)

    Zhou, Yuhang; Zhu, Yin; Lin, Lili; Zhang, Yulong; Zheng, Jianfeng; Liu, Xiaohua; Feng, Xiaoming

    2014-12-08

    N,N'-Dioxide/nickel(II) complexes have been developed to catalyze the inverse-electron-demand hetero-Diels-Alder reaction of β,γ-unsaturated α-ketoesters with acyclic enecarbamates. After detailed screening of the reaction parameters, mild optimized reaction conditions were established, affording 3,4-dihydro-2H-pyranamines in up to 99 % yield, 99 % ee and more than 95:5 d.r. The catalytic system was also efficient for β-substituted acyclic enecarbamates, affording more challenging 2,3,4-trisubstituted 3,4-dihydro-2H-pyranamine with three contiguous stereogenic centers in excellent yields, diastereoselectivities, and enantioselectivities. The reaction could be scaled up to a gram scale with no deterioration of either enantioselectivity or yield. Based on these experiments and on previous reports, a possible transition state was proposed. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Vicinal Diboronates in High Enantiomeric Purity through Tandem Site-Selective NHC–Cu-Catalyzed Boron-Copper Additions to Terminal Alkynes

    Science.gov (United States)

    Lee, Yunmi; Jang, Hwanjong; Hoveyda, Amir H.

    2009-01-01

    A Cu-catalyzed protocol for conversion of terminal alkynes to enantiomerically enriched diboronates is reported. In a single vessel, a site-selective hydroboration of an alkyne leads to the corresponding terminal vinylboronate, which undergoes a second site-selective and enantioselective hydroboration. Reactions proceed in the presence of two equivalents of commercially available bis(pinacolato)diboron [B2(pin)2] and 5–7.5 mol % of a chiral bidentate imidazolinium salt, affording diboronates in 60–93% yield and up to 97.5:2.5 enantiomeric ratio (er). The enantiomerically enriched products can be functionalized to afford an assortment of versatile organic molecules. Enynes are converted to unsaturated diboronates with high chemo- (>98% reaction of alkyne; <2% at alkene) and enantioselectivity (e.g., 94.5:5.5 er). PMID:19968273

  2. Caffeine-catalyzed gels.

    Science.gov (United States)

    DiCiccio, Angela M; Lee, Young-Ah Lucy; Glettig, Dean L; Walton, Elizabeth S E; de la Serna, Eva L; Montgomery, Veronica A; Grant, Tyler M; Langer, Robert; Traverso, Giovanni

    2018-07-01

    Covalently cross-linked gels are utilized in a broad range of biomedical applications though their synthesis often compromises easy implementation. Cross-linking reactions commonly utilize catalysts or conditions that can damage biologics and sensitive compounds, producing materials that require extensive post processing to achieve acceptable biocompatibility. As an alternative, we report a batch synthesis platform to produce covalently cross-linked materials appropriate for direct biomedical application enabled by green chemistry and commonly available food grade ingredients. Using caffeine, a mild base, to catalyze anhydrous carboxylate ring-opening of diglycidyl-ether functionalized monomers with citric acid as a tri-functional crosslinking agent we introduce a novel poly(ester-ether) gel synthesis platform. We demonstrate that biocompatible Caffeine Catalyzed Gels (CCGs) exhibit dynamic physical, chemical, and mechanical properties, which can be tailored in shape, surface texture, solvent response, cargo release, shear and tensile strength, among other potential attributes. The demonstrated versatility, low cost and facile synthesis of these CCGs renders them appropriate for a broad range of customized engineering applications including drug delivery constructs, tissue engineering scaffolds, and medical devices. Copyright © 2018 The Authors. Published by Elsevier Ltd.. All rights reserved.

  3. Microindentation hardness evaluation of iridium alloy clad vent set cups

    International Nuclear Information System (INIS)

    Ulrich, G.B.; DeRoos, L.F.; Stinnette, S.E.

    1993-01-01

    An iridium alloy, DOP-26, is used as cladding for 238 PuO 2 fuel in radioisotope heat sources for space power systems. Presently, DOP-26 iridium alloy clad vent sets (CVS) are being manufactured at the Oak Ridge Y-12 Plant for potential use in the National Aeronautics and Space Administration's Cassini mission to Saturn. Wrought/ground/stress relieved blanks are warm formed into CVS cups. These cups are then annealed to recrystallize the material for subsequent fabrication/assembly operations as well as for final use. One of the cup manufacturing certification requirements is to test for Vickers microindentation hardness. New microindentation hardness specification limits, 210 to 310 HV, have been established for a test load of 1000 grams-force (gf). The original specification limits, 250 to 350 HV, were for 200 gf testing. The primary reason for switching to a higher test load was to reduce variability in the test data. The DOP-26 alloy exhibits microindentation hardness load dependence, therefore, new limits were needed for 1000 gf testing. The new limits were established by testing material from 15 CVS cups using 200 gf and 1000 gf loads and then statistically analyzing the data. Additional work using a Knoop indenter and a 10 gf load indicated that the DOP-26 alloy grain boundaries have higher hardnesses than the grain interiors

  4. Iridium-192 implants in the treatment of tonsillar region malignancies

    International Nuclear Information System (INIS)

    Puthawala, A.A.; Syed, A.M.; Gates, T.C.

    1985-01-01

    A total of 127 patients with histologically proved diagnosis of carcinoma of the tonsillar region and soft palate were treated over the past ten years utilizing interstitial iridium-192 implants. Eighty patients were treated for primary tumors and 47 patients for either recurrent or persistent tumors after definitive irradiation and/or surgery. All patients with primary tumors were treated by a combination of external megavoltage irradiation and interstitial iridium-192 implants, whereas patients with recurrent tumors were treated by interstitial implants alone. In the primary group, 95% of patients with T1 and T2 lesions and 79% with T3 and T4 lesions achieved complete local tumor control. The three-year absolute disease-free survival rate was 72%. Seventy-five percent local tumor control was obtained in patients with recurrent disease, with two-year absolute disease-free survival of 42%. Treatment-related complications such as soft-tissue necrosis or osteoradionecrosis occurred in 6% of patients in the primary group and 23% in recurrent group. This treatment regimen offers an excellent locoregional control with no significant functional or esthetic impairment. Most patients with primary lesions who fail this regimen can be salvaged by surgery or reirradiation using interstitial implants

  5. Dosimetry of wires and single ribbons of Iridium 192

    International Nuclear Information System (INIS)

    Mazzucco, L.D.

    1998-01-01

    The objective of this work is in order to present in table formats the dosimetry of wires and single ribbons of Iridium with lengths 1-12 cm for each one linear source along the bisector which is perpendicular at tissue sources (water) computed for linear activity 1 mCi/cm in the case of wires, and 1 mCi/seed for ribbons. The above tables are of direct use, adaptable at particular cases so they facilitate logarithmic graphics of doses in function of the distance for interpolation and use in the treatments planning. It was shown that for two sources with identical linear activity and total length, one of the equidistant seeds at 1 cm (ribbon) and one wire on the other hand, the differences in dose rates in near positions can be about the 15% so corroborating that it is not possible to use wire tables for seeds neither vice versa. Moreover it was elaborated tables of practical direct use for dose rate in water at c Gy/hr for wires and Ribbons 1-12 cm length and from 0.5-10 cm of distance in the perpendicular bisector at the Iridium implant. (Author)

  6. Microindentation hardness evaluation of iridium alloy clad vent set cups

    International Nuclear Information System (INIS)

    Ulrich, G.B.; DeRoos, L.F.; Stinnette, S.E.

    1992-01-01

    An iridium alloy, DOP-26, is used as cladding for 238 PuO 2 fuel in radioisotope heat sources for space power systems. Presently, DOP-26 iridium alloy clad vent sets (CVS) are being manufactured at the Oak Ridge Y-12 Plant for potential use in the National Aeronautics and Space Administration's Cassini mission to Saturn. Wrought/ground/stress relieved blanks are warm formed into CVS cups. These cups are then annealed to recrystallize the material for subsequent fabrication/assembly operations as well as for final use. One of the cup manufacturing certification requirements is to test for Vickers microindentation hardness. New microindentation hardness specification limits, 210 to 310 HV, have been established for a test load of 1000 grams-force (gf). The original specification limits, 250 to 350 HV, were for 200 gf testing. The primary reason for switching to a higher test load was to reduce variability in the test data. The DOP-26 alloy exhibits microindentation hardness load dependence, therefore, new limits were needed for 1000 gf testing. The new limits were established by testing material from 15 CVS cups using 200 gf and 1000 gf loads and then statistically analyzing the data. Additional work using a Knoop indenter and a 10 gf load indicated that the DOP-26 alloy grain boundaries have higher hardnesses than the grain interiors

  7. Incorporation of iridium into electrodeposited rhenium–nickel alloys

    International Nuclear Information System (INIS)

    Cohen Sagiv, Maayan; Eliaz, Noam; Gileadi, Eliezer

    2013-01-01

    Rhenium (Re), a refractory metal that has gained significant recognition as a high performance engineering material, is mostly used in military, aircraft and aerospace applications, as well as for catalysis in the petrochemical industry. However, its performance at high temperature in humid air is limited by the formation of rhenium heptoxide (Re 2 O 7 ), which penetrates the grain boundaries and causes brittleness. Improvement of this is being sought through the incorporation of iridium (Ir) into Re deposits. To this end, suitable plating baths for Re–Ir–Ni coatings were developed. These alloys were deposited from different aqueous solutions on copper substrates under galvanostatic conditions, in a three-electrode cell. The plating bath consisted of iridium tri-chloride, ammonium perrhenate and nickel sulfamate as the electroactive species, and citric acid as the complexing agent. The effects of bath composition and operating conditions on the Faradaic efficiency (FE), partial current densities, as well as on the thickness of the coatings and their composition were studied. Re–Ir–Ni coatings as thick as 18 μm, with Re-content as high as 73 at.% and Ir-content as high as 29 at.%, were obtained, using different plating baths. A mechanism of the electrochemical process was suggested. It was found that both an HCP Ir 0.4 Re 0.6 phase and an HCP Ni phase with nanometric crystallites were formed, possibly together with a hexagonal nickel hydride (Ni 2 H) phase

  8. Dynamic high-temperature characterization of an iridium alloy in tension

    Energy Technology Data Exchange (ETDEWEB)

    Song, Bo [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Nelson, Kevin [Sandia National Lab. (SNL-CA), Livermore, CA (United States); Jin, Helena [Sandia National Lab. (SNL-CA), Livermore, CA (United States); Lipinski, Ronald J. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Bignell, John [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Ulrich, G. B. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); George, E. P. [Ruhr Univ., Bochum (Germany)

    2015-09-01

    Iridium alloys have been utilized as structural materials for certain high-temperature applications, due to their superior strength and ductility at elevated temperatures. The mechanical properties, including failure response at high strain rates and elevated temperatures of the iridium alloys need to be characterized to better understand high-speed impacts at elevated temperatures. A DOP-26 iridium alloy has been dynamically characterized in compression at elevated temperatures with high-temperature Kolsky compression bar techniques. However, the dynamic high-temperature compression tests were not able to provide sufficient dynamic high-temperature failure information of the iridium alloy. In this study, we modified current room-temperature Kolsky tension bar techniques for obtaining dynamic tensile stress-strain curves of the DOP-26 iridium alloy at two different strain rates (~1000 and ~3000 s-1) and temperatures (~750°C and ~1030°C). The effects of strain rate and temperature on the tensile stress-strain response of the iridium alloy were determined. The DOP-26 iridium alloy exhibited high ductility in stress-strain response that strongly depended on both strain rate and temperature.

  9. A preliminary study of factors affecting the calibration stability of the iridium versus iridium-40 percent rhodium thermocouple

    Science.gov (United States)

    Ahmed, Shaffiq; Germain, Edward F.; Daryabeigi, Kamran; Alderfer, David W.; Wright, Robert E.

    1987-01-01

    An iridium versus iridium-40% rhodium thermocouple was studied. Problems associated with the use of this thermocouple for high temperature applications (up to 2000 C) were investigated. The metallurgical studies included X-ray, macroscopic, resistance, and metallographic studies. The thermocouples in the as-received condition from the manufacturer revealed large amounts of internal stress caused by cold working during manufacturing. The thermocouples also contained a large amount of inhomogeneities and segregations. No phase transformations were observed in the alloy up to 1100 C. It was found that annealing the thermocouple at 1800 C for two hours, and then at 1400 C for 2 to 3 hours yielded a fine grain structure, relieving some of the strains, and making the wire more ductile. It was also found that the above annealing procedure stabilized the thermal emf behavior of the thermocouple for application below 1800 C (an improvement from + or - 1% to + or - 0.02% within the range of the test parameters used).

  10. Catalyzing alignment processes

    DEFF Research Database (Denmark)

    Lauridsen, Erik Hagelskjær; Jørgensen, Ulrik

    2004-01-01

    This paper describes how environmental management systems (EMS) spur the circulation of processes that support the constitution of environmental issues as specific environ¬mental objects and objectives. EMS catalyzes alignmentprocesses that produce coherence among the different elements involved......, the networks of environmental professionals that work in the environmental organisation, in consulting and regulatory enforcement, and dominating business cultures. These have previously been identified in the literature as individually significant in relation to the evolving environmental agendas...... they are implemented in and how the changing context is reflected in the environmental objectives that are established and prioritised. Our argument is, that the ability of the standard to achieve an impact is dependant on the constitution of ’coherent’ environmental issues in the context, where the management system...

  11. Development of Environment-Friendly Insecticides Based on Enantioselectivity: Bifenthrin as a Case.

    Science.gov (United States)

    Qian, Yi; Zhou, Peixue; Zhang, Quan

    2017-01-01

    Chiral insecticides significantly contribute to the environmental pollutions recently. As the development of industry and agriculture, increasing number of chiral insecticides are to be introduced into the market. However, their enantioselective toxicology to ecosystem still remains uncertain. In this review, we embarked on a structured search of bibliographic databases for peer-reviewed articles regarding the enantioselective effects of bifenthrin, a typical chiral insecticide, on both target and non-target species. With this enantioselective property of chiral insecticides, they often exhibit adverse effects on non-target species enantioselectively. Specifically, the enantioselective effects of bifenthrin on target and non-target organisms were discussed. In target species, R-bifenthrin exerts more significant activities in deinsectization, compared with S-bifenthrin. On the other hand, Sbifenthrin is more toxic to non-target species than R-bifenthrin, which suggests that the application of sole enantiomer is more efficient and environment-friendly than that of racemate. This review confirms the choice of environment-friendly insecticides from the perspective of the enantioselectivity of chiral insecticides. To make insecticides more efficient to target species and less toxic to non-target species, further research should be done to investigated the potential effects of targetactive enantiomers on non-target organisms as well as the enantioselective fate of enantiomers in multiple environmental matrix.

  12. Metal-Free Catalytic Enantioselective C–B Bond Formation: (Pinacolato)boron Conjugate Additions to α,β-Unsaturated Ketones, Esters, Weinreb Amides and Aldehydes Promoted by Chiral N-Heterocyclic Carbenes

    Science.gov (United States)

    Wu, Hao; Radomkit, Suttipol; O’Brien, Jeannette M.; Hoveyda, Amir H.

    2012-01-01

    The first broadly applicable metal-free enantioselective method for boron conjugate addition (BCA) to α,β-unsaturated carbonyls is presented. The C–B bond forming reactions are promoted in the presence of 2.5–7.5 mol % of a readily accessible C1-symmetric chiral imidazolinium salt, which is converted, in situ, to the catalytically active diastereo- and enantiomerically pure N-heterocyclic carbene (NHC) by the common organic base 1,8-diazabicyclo[5.4.0]undec-7-ene (dbu). In addition to the commercially available bis(pinacolato)diboron [B2(pin)2], and in contrast to reactions with the less sterically demanding achiral NHCs, the presence of MeOH is required for high efficiency. Acyclic and cyclic α,β-unsaturated ketones, as well as acyclic esters, Weinreb amides and aldehydes can serve as suitable substrates; the desired β-boryl carbonyls are isolated in up to 94% yield and >98:2 enantiomer ratio (er). Transformations are often carried out at ambient temperature. In certain cases, such as when the relatively less reactive unsaturated amides are used, elevated temperatures are required (50–66 °C); nonetheless, reactions remain highly enantioselective. The utility of the NHC-catalyzed method is demonstrated through comparison with the alternative Cu-catalyzed protocols; in cases involving a polyfunctional substrate, unique profiles in chemoselectivity are exhibited by the metal-free approach (e.g., conjugate addition vs reaction with an alkyne, allene or aldehyde). PMID:22559866

  13. Iridium Oxide pH Sensor Based on Stainless Steel Wire for pH Mapping on Metal Surface

    Science.gov (United States)

    Shahrestani, S.; Ismail, M. C.; Kakooei, S.; Beheshti, M.; Zabihiazadboni, M.; Zavareh, M. A.

    2018-03-01

    A simple technique to fabricate the iridium oxide pH sensor is useful in several applications such as medical, food processing and engineering material where it is able to detect the changes of pH. Generally, the fabrication technique can be classified into three types: electro-deposition iridium oxide film (EIrOF), activated iridium oxide film (AIROF) and sputtering iridium oxide film (SIROF). This study focuses on fabricating electrode, calibration and test. Electro-deposition iridium oxide film is a simple and effective method of fabricating this kind of sensor via cyclic voltammetry process. The iridium oxide thick film was successfully electrodeposited on the surface of stainless steel wire with 500 cycles of sweep potential. A further analysis under FESEM shows detailed image of iridium oxide film which has cauliflower-liked microstructure. EDX analysis shows the highest element present are iridium and oxygen which concluded that the process is successful. The iridium oxide based pH sensor has shown a good performance in comparison to conventional glass pH sensor when it is being calibrated in buffer solutions with 2, 4, 7 and 9 pH values. The iridium oxide pH sensor is specifically designed to measure the pH on the surface of metal plate.

  14. Hydrogenation of ethene catalyzed by Ir atom deposited on γ-Al2O3(001) surface: From ab initio calculations

    International Nuclear Information System (INIS)

    Chen, Yongchang; Sun, Zhaolin; Song, Lijuan; Li, Qiang; Xu, Ming

    2012-01-01

    Ethene hydrogenation reaction, catalyzed by an iridium atom adsorbed on γ-Al 2 O 3 (001) surface, is studied via ab initio calculations based on density functional theory (DFT). The catalyzed reaction process and activation energy are compared with the counterparts of a reaction occurs in vacuum condition. It is found that the activation energy barrier is substantially lowered by the adsorbed Ir atom on the γ-Al 2 O 3 (001). The catalyzed reaction is modeled in two steps: (1) Hydrogen molecular dissolution and then bonded with C 2 H 4 molecular. (2) Desorption of the C 2 H 6 molecular from the surface. -- Highlights: ► The ethene hydrogenation reaction is simulated with nudged elastic band methods. ► The catalytic effect of the Ir atom on γ-Al 2 O 3 (001) surface is modeled. ► Details of the catalytic reaction are exhibited.

  15. Enantioselective synthesis of α-oxy amides via Umpolung amide synthesis.

    Science.gov (United States)

    Leighty, Matthew W; Shen, Bo; Johnston, Jeffrey N

    2012-09-19

    α-Oxy amides are prepared through enantioselective synthesis using a sequence beginning with a Henry addition of bromonitromethane to aldehydes and finishing with Umpolung Amide Synthesis (UmAS). Key to high enantioselection is the finding that ortho-iodo benzoic acid salts of the chiral copper(II) bis(oxazoline) catalyst deliver both diastereomers of the Henry adduct with high enantiomeric excess, homochiral at the oxygen-bearing carbon. Overall, this approach to α-oxy amides provides an innovative complement to alternatives that focus almost entirely on the enantioselective synthesis of α-oxy carboxylic acids.

  16. An iron-57 Moessbauer spectroscopic study of titania-supported iron- and iron-iridium catalysts

    International Nuclear Information System (INIS)

    Berry, F.J.; Jobson, S.

    1992-01-01

    57 Fe Moessbauer spectroscopy shows that titania-supported iron is reduced by treatment in hydrogen at significantly lower temperatures than corresponding silica- and alumina-supported catalysts. The metallic iron formed under hydrogen at 600deg C is partially converted to carbide by treatment in carbon monoxide and hydrogen. In contrast to its alumina- and silica-supported counterparts, the remainder of the titania-supported iron is unchanged by this gaseous mixture. The 57 Fe Moessbauer spectra of EXAFS show that iron and iridium in the titania-supported iron-iridium catalysts are reduced in hydrogen at even lower temperatures and, after treatment at 600deg C, are predominantly present as the iron-iridium alloy. The treatment of these reduced catalysts in carbon monoxide and hydrogen is shown by Moessbauer spectroscopy and EXAFS to induce the segregation of iron from the iron-iridium alloy and its conversion to iron oxide. (orig.)

  17. Effect of the lead screen in the radiographic image using iridium 192 as a source

    International Nuclear Information System (INIS)

    Garate Rojas, M.

    1983-01-01

    It's presented the effect of the lead screen in the image obtained on an impressionable film used in industrial gammagraphy. The source used was Iridium 192 and the tests were simulated like a real inspection. (E.G.) [pt

  18. Iridium-catalyst-based autonomous bubble-propelled graphene micromotors with ultralow catalyst loading.

    Science.gov (United States)

    Wang, Hong; Sofer, Zdeněk; Eng, Alex Yong Sheng; Pumera, Martin

    2014-11-10

    A novel concept of an iridium-based bubble-propelled Janus-particle-type graphene micromotor with very high surface area and with very low catalyst loading is described. The low loading of Ir catalyst (0.54 at %) allows for fast motion of graphene microparticles with high surface area of 316.2 m(2)  g(-1). The micromotor was prepared with a simple and scalable method by thermal exfoliation of iridium-doped graphite oxide precursor composite in hydrogen atmosphere. Oxygen bubbles generated from the decomposition of hydrogen peroxide at the iridium catalytic sites provide robust propulsion thrust for the graphene micromotor. The high surface area and low iridium catalyst loading of the bubble-propelled graphene motors offer great possibilities for dramatically enhanced cargo delivery. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Influence of iridium on the reactivity of LaFeO3 base perovskites

    DEFF Research Database (Denmark)

    Kindermann, L.; Das, D.; Bahadur, D.

    1998-01-01

    The influence of iridium on the reactivity of powder mixtures made of perovskites and 8 mol% yttria stabilized zirconia (8 YSZ) is reported. Iridium is added to the perovskites of the composition (La0.6M0.4)(z)Fe0.8TM0.2O3-delta (M = Sr, Ca; TM = Mn, Co; z = 0.90, 1.00) via the gaseous phase....... Iridium is present in the perovskite lattice as Ir4+ replacing iron as is evident from XRD and TEM/EDX results. Compatibility studies carried out at 1000 degrees C demonstrate that iridium has considerable influence on the reactivity. The results are discussed with respect to the stability...... of the perovskites, thermodynamic activities, Ir(IV)-O bonding, tolerance factor and oxygen migration....

  20. Low-Stress Iridium Coatings for Thin-Shell X-Ray Telescopes, Phase II

    Data.gov (United States)

    National Aeronautics and Space Administration — We propose to develop and commercialize a new type of low-stress iridium (Ir) X-ray mirror coating technology that can be used for the construction of...

  1. Postimpact examinations of three DOP 4 iridium shells from simulant fuel sphere assemblies

    International Nuclear Information System (INIS)

    Cramer, E.M.; Hecker, S.S.

    1975-12-01

    Three fuel sphere assemblies, with thoria in doped iridium containment shells, were examined after a simulated earth impact from an aborted orbital mission of a multihundred-watt thermoelectric heat source. The extent of deformation of each unit was measured. Damage to the containment shells was minimal in comparison to that in undoped iridium. Metallographic sections from critical areas indicated that superficial grain boundary cracking in weld zones and microscopic cracking in regions of maximum diameter had occurred in addition to local thinning and coining. The improved properties of the doped iridium are attributed to the retention of a small grain size and to an additional fracture resistance over iridium of a comparable grain size, imparted by either a change in grain boundary chemistry or the flow characteristics of the doped material

  2. Electron beam welding of iridium heat source capsules

    International Nuclear Information System (INIS)

    Mustaleski, T.M.; Yearwood, J.C.; Burgan, C.E.; Green, L.A.

    1991-01-01

    The development of the welding procedures for the production of DOP-26 iridium alloy cups for heat source encapsulation is described. All the final assembly welds were made using the electron beam welding process. The welding of the 0.13-mm weld shield required the use of computer controlled X-Y table and a run-off tab. Welding of the frit vent to the cup required that a laser weld be made to hold the frit assembly edges together for the final electron beam weld. Great care is required in tooling design and beam placement to achieve acceptable results. Unsuccessful attempts to use laser beam welding for heat shield butt weld are discussed

  3. Diastereoselective and enantioselective reduction of tetralin-1,4-dione

    Directory of Open Access Journals (Sweden)

    2008-10-01

    Full Text Available BackgroundThe chemistry of tetralin-1,4-dione, the stable tautomer of 1,4-dihydroxynaphthalene, has not been explored previously. It is readily accessible and offers interesting opportunities for synthesis.ResultsThe title reactions were explored. L-Selectride reduced the diketone to give preferentially the cis-diol (d.r. 84 : 16. Red-Al gave preferentially the trans-diol (d.r. 13 : 87. NaBH4, LiAlH4, and BH3 gave lower diastereoselectivities (yields: 76–98%. Fractional crystallization allowed isolation of the cis-diol and the trans-diol (55% and 66% yield, respectively. Borane was used to cleanly give the mono-reduction product. Highly enantioselective CBS reductions afforded the trans-diol (72% yield, 99% ee and the mono-reduction product (81%, 95% ee.ConclusionDiastereoselective and enantioselective reductions of the unexplored tetralin-1,4-dione provides a very convenient entry into a number of synthetically highly attractive 1,4-tetralindiols and 4-hydroxy-1-tetralone.

  4. Diastereoselective and enantioselective reduction of tetralin-1,4-dione.

    Science.gov (United States)

    Kündig, E Peter; Enriquez-Garcia, Alvaro

    2008-01-01

    The chemistry of tetralin-1,4-dione, the stable tautomer of 1,4-dihydroxynaphthalene, has not been explored previously. It is readily accessible and offers interesting opportunities for synthesis. The title reactions were explored. L-Selectride reduced the diketone to give preferentially the cis-diol (d.r. 84 : 16). Red-Al gave preferentially the trans-diol (d.r. 13 : 87). NaBH(4), LiAlH(4), and BH(3) gave lower diastereoselectivities (yields: 76-98%). Fractional crystallization allowed isolation of the cis-diol and the trans-diol (55% and 66% yield, respectively). Borane was used to cleanly give the mono-reduction product. Highly enantioselective CBS reductions afforded the trans-diol (72% yield, 99% ee) and the mono-reduction product (81%, 95% ee). Diastereoselective and enantioselective reductions of the unexplored tetralin-1,4-dione provides a very convenient entry into a number of synthetically highly attractive 1,4-tetralindiols and 4-hydroxy-1-tetralone.

  5. Enantioselective degradation and enantiomerization of indoxacarb in soil.

    Science.gov (United States)

    Sun, Dali; Pang, Junxiao; Qiu, Jing; Li, Li; Liu, Chenglan; Jiao, Bining

    2013-11-27

    In this study, the enantioselective degradation and enantiomerizaton of indoxacarb were investigated in two soils under nonsterilized and sterilized conditions using a chiral OD-RH column on a reversed-phase HPLC. Under nonsterilized conditions, the degradation of indoxacarb in two soils was enantioselective. In acidic soil, the half-lives of R-(-)- and S-(+)-indoxacarb were 10.43 and 14.00 days, respectively. Acidic soil was preferential to the degradation of R-(-)-indoxacarb. In alkaline soil, the half-lives of R-(-)- and S-(+)-indoxacarb were 12.14 and 4.88 days, respectively. S-(+)-Indoxacarb was preferentially degraded. Under sterilized conditions, approximately 5-10% of the initial concentration degraded after 75 days of incubation in acidic soil, whereas in alkaline soil, approximately half of the initial concentration degraded due to chemical hydrolysis under alkaline conditions. Enantiomerization was also discovered in acidic and alkaline soils. The results showed that mutual transformation existed between two enantiomers and that S-(+)-indoxacarb had a significantly higher inversion rate to R-(-)-indoxacarb than its antipode.

  6. Chiral separation and enantioselective degradation of vinclozolin in soils.

    Science.gov (United States)

    Liu, Hui; Liu, Donghui; Shen, Zhigang; Sun, Mingjing; Zhou, Zhiqiang; Wang, Peng

    2014-03-01

    Vinclozolin is a chiral fungicide with potential environmental problems. The chiral separation of the enantiomers and enantioselective degradation in soil were investigated in this work. The enantiomers were separated by high-performance liquid chromatography (HPLC) on Chiralpak IA, IB, and AZ-H chiral columns under normal phase and the influence of the mobile phase composition on the separation was also studied. Complete resolutions were obtained on all three chiral columns under optimized conditions with the same elution order of (+)/(-). The residual analysis of the enantiomers in soil was conducted using accelerate solvent extraction followed by HPLC determination. The recoveries of the enantiomers ranged from 85.7-105.7% with relative standard deviation (SD) of 0.12-3.83%, and the limit of detection (LOD) of the method was 0.013 µg/g. The results showed that the degradations of vinclozolin enantiomers in the soils followed first-order kinetics. Preferential degradation of the (-)-enantiomer was observed only in one soil with the largest |ES| value of 0.047, and no obvious enantioselective degradation was observed in other soils. It was found that the persistence of vinclozolin in soil was related to pH values based on the half-lives. The two enantiomers disappeared about 8 times faster in basic soils than that in neutral or acidic soils. © 2014 Wiley Periodicals, Inc.

  7. Enantiomeric separation of iridium (III) complexes using HPLC chiral stationary phases based on amylose derivatives

    International Nuclear Information System (INIS)

    Kim, Hee Eun; Seo, Na Hyeon; Hyun, Myung Ho

    2016-01-01

    Cyclometalated iridium (III) complexes formed with three identical cyclometalating (C-N) ligands (homoleptic) or formed with two cyclometalating (C-N) ligands and one ancillary (LX) ligand (heteroleptic) have been known as highly phosphorescent materials and, thus, they have been utilized as efficient phosphorescent dopants in organic light emitting diodes (OLEDs) 1–3 or as effective phosphorescent chemosensors. 4–7 Cylometalated iridium (III) complexes are chiral compounds consisting of lambda (Λ, left-handed) and delta (Δ, right-handed) isomers. Racemic cyclometa- lated iridium (III) complexes emit light with no net polarization, but optically active cyclometalated iridium (III) complexes emit circularly polarized light. 8,9 Circularly polarized light can be used in various fields including highly efficient three dimensional electronic devices, photo nic devices for optical data storage, biological assays, and others. 8,9 In order to obtain optically active cylometalated iridium (III) complexes and to determine the enantiomeric composition of optically active cylometalated iridium (III) complexes, liquid chromatogr aphic enantiomer separation method on chiral stationary phases (CSPs) has been used. For example, Okamoto and coworkers first reported the high performance liquid chromatographic (HPLC) direct enantiomeric separation of two homoleptic cylometalated iridium (III) complexes on immobilized amylose tris(3,5- dimethylphenylcarbamate) (Chiralpak IA), coated cellulose tris(3,5-dimethylphenylcarbamate) (Chiralc el OD), and coated cellulose tris(4-methylbenzoate) (Chiralce l OJ). 10 Supercritical fluid chromatography (SFC) was also used by Bernhard and coworkers for the enantiomeric separation of cylometalated iridium (III) complexes on coated amylose tris(3,5-dimethylphenylcarbamate) (Chiralpak AD-H). 8 However, the general use of the HPLC method for the direct enantiomeric separation of homoleptic

  8. Enantiomeric separation of iridium (III) complexes using HPLC chiral stationary phases based on amylose derivatives

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Hee Eun; Seo, Na Hyeon; Hyun, Myung Ho [Dept. of Chemistry and Chemistry Institute for Functional Materials, Pusan National University, Busan (Korea, Republic of)

    2016-12-15

    Cyclometalated iridium (III) complexes formed with three identical cyclometalating (C-N) ligands (homoleptic) or formed with two cyclometalating (C-N) ligands and one ancillary (LX) ligand (heteroleptic) have been known as highly phosphorescent materials and, thus, they have been utilized as efficient phosphorescent dopants in organic light emitting diodes (OLEDs) 1–3 or as effective phosphorescent chemosensors. 4–7 Cylometalated iridium (III) complexes are chiral compounds consisting of lambda (Λ, left-handed) and delta (Δ, right-handed) isomers. Racemic cyclometa- lated iridium (III) complexes emit light with no net polarization, but optically active cyclometalated iridium (III) complexes emit circularly polarized light. 8,9 Circularly polarized light can be used in various fields including highly efficient three dimensional electronic devices, photo nic devices for optical data storage, biological assays, and others. 8,9 In order to obtain optically active cylometalated iridium (III) complexes and to determine the enantiomeric composition of optically active cylometalated iridium (III) complexes, liquid chromatogr aphic enantiomer separation method on chiral stationary phases (CSPs) has been used. For example, Okamoto and coworkers first reported the high performance liquid chromatographic (HPLC) direct enantiomeric separation of two homoleptic cylometalated iridium (III) complexes on immobilized amylose tris(3,5- dimethylphenylcarbamate) (Chiralpak IA), coated cellulose tris(3,5-dimethylphenylcarbamate) (Chiralc el OD), and coated cellulose tris(4-methylbenzoate) (Chiralce l OJ). 10 Supercritical fluid chromatography (SFC) was also used by Bernhard and coworkers for the enantiomeric separation of cylometalated iridium (III) complexes on coated amylose tris(3,5-dimethylphenylcarbamate) (Chiralpak AD-H). 8 However, the general use of the HPLC method for the direct enantiomeric separation of homoleptic.

  9. Iridium-Knife: Another knife in radiation oncology.

    Science.gov (United States)

    Milickovic, Natasa; Tselis, Nikolaos; Karagiannis, Efstratios; Ferentinos, Konstantinos; Zamboglou, Nikolaos

    Intratarget dose escalation with superior conformity is a defining feature of three-dimensional (3D) iridium-192 ( 192 Ir) high-dose-rate (HDR) brachytherapy (BRT). In this study, we analyzed the dosimetric characteristics of interstitial 192 Ir HDR BRT for intrathoracic and cerebral malignancies. We examined the dose gradient sharpness of HDR BRT compared with that of linear accelerator-based stereotactic radiosurgery and stereotactic body radiation therapy, usually called X-Knife, to demonstrate that it may as well be called a Knife. Treatment plans for 10 patients with recurrent glioblastoma multiforme or intrathoracic malignancies, five of each entity, treated with X-Knife (stereotactic radiosurgery for glioblastoma multiforme and stereotactic body radiation therapy for intrathoracic malignancies) were replanned for simulated HDR BRT. For 3D BRT planning, we used identical structure sets and dose prescription as for the X-Knife planning. The indices for qualitative treatment plan analysis encompassed planning target volume coverage, conformity, dose falloff gradient, and the maximum dose-volume limits to different organs at risk. Volume coverage in HDR plans was comparable to that calculated for X-Knife plans with no statistically significant difference in terms of conformity. The dose falloff gradient-sharpness-of the HDR plans was considerably steeper compared with the X-Knife plans. Both 3D 192 Ir HDR BRT and X-Knife are effective means for intratarget dose escalation with HDR BRT achieving at least equal conformity and a steeper dose falloff at the target volume margin. In this sense, it can reasonably be argued that 3D 192 Ir HDR BRT deserves also to be called a Knife, namely Iridium-Knife. Copyright © 2017 American Brachytherapy Society. Published by Elsevier Inc. All rights reserved.

  10. Single step radiolytic synthesis of iridium nanoparticles onto graphene oxide

    International Nuclear Information System (INIS)

    Rojas, J.V.; Molina Higgins, M.C.; Toro Gonzalez, M.; Castano, C.E.

    2015-01-01

    Graphical abstract: - Highlights: • Ir nanoparticles were synthesized through a single step gamma irradiation process. • Homogeneously distributed Ir nanoparticles on graphene oxide are ∼2.3 nm in size. • Ir−O bonds evidenced the interaction of the nanoparticles with the support. - Abstract: In this work a new approach to synthesize iridium nanoparticles on reduced graphene oxide is presented. The nanoparticles were directly deposited and grown on the surface of the carbon-based support using a single step reduction method through gamma irradiation. In this process, an aqueous isopropanol solution containing the iridium precursor, graphene oxide, and sodium dodecyl sulfate was initially prepared and sonicated thoroughly to obtain a homogeneous dispersion. The samples were irradiated with gamma rays with energies of 1.17 and 1.33 MeV emitted from the spontaneous decay of the 60 Co irradiator. The interaction of gamma rays with water in the presence of isopropanol generates highly reducing species homogeneously distributed in the solution that can reduce the Ir precursor down to a zero valence state. An absorbed dose of 60 kGy was used, which according to the yield of reducing species is sufficient to reduce the total amount of precursor present in the solution. This novel approach leads to the formation of 2.3 ± 0.5 nm Ir nanoparticles distributed along the surface of the support. The oxygenated functionalities of graphene oxide served as nucleation sites for the formation of Ir nuclei and their subsequent growth. XPS results revealed that the interaction of Ir with the support occurs through Ir−O bonds.

  11. Synthesis and characterization of low-valence actinide phosphide tellurides and ternary selenium-halide iridium complexes; Synthese und Charakterisierung niedervalenter Actinoidphosphidtelluride und ternaerer Selen-Halogenid-Komplexe des Iridiums

    Energy Technology Data Exchange (ETDEWEB)

    Stolze, Karoline

    2016-04-07

    The thesis on the synthesis and characterization of low-valence actinide phosphide tellurides and ternary selenium-halide iridium complexes includes two parts: a description of the experimental synthesis of UPTe and U2PTe2O and ThPTe and the synthesis of selenium-chloride iridium complexes and selenium-bromide iridium complexes. The characterization included X-ray diffraction and phase studies.

  12. 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.

  13. 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.

  14. Asymmetric Synthesis of Hydrocarbazoles Catalyzed by an Octahedral Chiral-at-Rhodium Lewis Acid.

    Science.gov (United States)

    Huang, Yong; Song, Liangliang; Gong, Lei; Meggers, Eric

    2015-12-01

    A bis-cyclometalated chiral-at-metal rhodium complex catalyzes the Diels-Alder reaction between N-Boc-protected 3-vinylindoles (Boc = tert-butyloxycarbonyl) and β-carboxylic ester-substituted α,β-unsaturated 2-acyl imidazoles with good-to-excellent regioselectivity (up to 99:1) and excellent diastereoselectivity (>50:1 d.r.) as well as enantioselectivity (92-99% ee) under optimized conditions. The rhodium catalyst serves as a chiral Lewis acid to activate the 2-acyl imidazole dienophile by two-point binding and overrules the preferred regioselectivity of the uncatalyzed reaction. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Dynamic High-Temperature Characterization of an Iridium Alloy in Compression at High Strain Rates

    Energy Technology Data Exchange (ETDEWEB)

    Song, Bo [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Experimental Environment Simulation Dept.; Nelson, Kevin [Sandia National Lab. (SNL-CA), Livermore, CA (United States). Mechanics of Materials Dept.; Lipinski, Ronald J. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Advanced Nuclear Fuel Cycle Technology Dept.; Bignell, John L. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Structural and Thermal Analysis Dept.; Ulrich, G. B. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Radioisotope Power Systems Program; George, E. P. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Radioisotope Power Systems Program

    2014-06-01

    Iridium alloys have superior strength and ductility at elevated temperatures, making them useful as structural materials for certain high-temperature applications. However, experimental data on their high-temperature high-strain-rate performance are needed for understanding high-speed impacts in severe elevated-temperature environments. Kolsky bars (also called split Hopkinson bars) have been extensively employed for high-strain-rate characterization of materials at room temperature, but it has been challenging to adapt them for the measurement of dynamic properties at high temperatures. Current high-temperature Kolsky compression bar techniques are not capable of obtaining satisfactory high-temperature high-strain-rate stress-strain response of thin iridium specimens investigated in this study. We analyzed the difficulties encountered in high-temperature Kolsky compression bar testing of thin iridium alloy specimens. Appropriate modifications were made to the current high-temperature Kolsky compression bar technique to obtain reliable compressive stress-strain response of an iridium alloy at high strain rates (300 – 10000 s-1) and temperatures (750°C and 1030°C). Uncertainties in such high-temperature high-strain-rate experiments on thin iridium specimens were also analyzed. The compressive stress-strain response of the iridium alloy showed significant sensitivity to strain rate and temperature.

  16. Formation of nano iridium oxide: material properties and neural cell culture

    International Nuclear Information System (INIS)

    Lee, In-Seop; Whang, Chung-Nam; Lee, Young-Hee; Hwan Lee, Gun; Park, Bong-Joo; Park, Jong-Chul; Seo, Won-Seon; Cui Fuzhai

    2005-01-01

    Iridium film with the thickness of 30 and 60 nm were formed on both Si wafer and commercially pure (CP) Ti by electron beam evaporation. The thin iridium film showed the identical charge injection capability with the bulk Ir. However, the charge injection value of iridium film was decreased with continuous potential cycling when the deposited iridium became depleted due to the formation of oxide. The number of cycles at which the charge injection value decreased was 800 and 1600 cycles for the 30- and 60-nm-thick Ir film, respectively. FE-SEM observations on the cross section of Ir film clearly showed the thicker iridium oxide was formed with the more potential cycling. Ar ion beam etching to substrates before deposition certainly improved the adhesion strength of Ir film enough to resist to the strain induced by the larger volume occupation of iridium oxide. Swiss 3T3 fibroblasts culture on Ir and Ir oxide showed no cytotoxicity. Also, embryonic cortical neural cell culture on electrode indicated neurons adhered and survived by the formation of neurofilament

  17. Optimisation of stabilised carboxylesterase NP for enantioselective hydrolysis of naproxen methyl ester

    CSIR Research Space (South Africa)

    Steenkamp, Lucia H

    2008-12-01

    Full Text Available Although the enantioselective kinetic resolution of ester racemates of the non-steroidal antiinflammatory drug naproxen ([2-(6-methoxy-2-naphthyl) propionic acid]) is a common demonstration for biocatalysis, the enantiomeric excess of the reactions...

  18. BIOACCUMULATION AND ENANTIOSELECTIVE BIOTRANSFORMATION OF FIPRONIL BY RAINBOW TROUT (ONCORHYNCHUS MYKISS)

    Science.gov (United States)

    Dietary accumulation and enantioselective biotransformation was determined for rainbow trout (Oncorhynchus mykiss) exposed to fipronil, a widely used chiral pesticide. Measurement of the fish carcass tissue (whole fish minus GI tract and liver) showed a rapid accumulation of fip...

  19. Purification and characterisation of a novel enantioselective epoxide hydrolase from Aspergillus niger M200

    Czech Academy of Sciences Publication Activity Database

    Kotík, Michael; Kyslík, Pavel

    2006-01-01

    Roč. 1760, - (2006), s. 245-252 ISSN 0006-3002 Institutional research plan: CEZ:AV0Z50200510 Keywords : epoxide hydrolase * enantioselectivity * aspergillus niger Subject RIV: EE - Microbiology, Virology

  20. Catalyzed deuterium fueled tokamak reactors

    International Nuclear Information System (INIS)

    Southworth, F.H.

    1977-01-01

    Catalyzed deuterium fuel presents several advantages relative to D-T. These are, freedom from tritium breeding, high charged particle power fraction and lowered neutron energy deposition in the blanket. Higher temperature operation, lower power densities and increased confinement are simultaneously required. However, the present study has developed designs which have capitalized upon the advantages of catalyzed deuterium to overcome the difficulties associated with the fuel while obtaining high efficiency

  1. Ruthenium Hydride/Brønsted Acid-Catalyzed Tandem Isomerization/N-Acyliminium Cyclization Sequence for the Synthesis of Tetrahydro-β-carbolines

    DEFF Research Database (Denmark)

    Hansen, Casper Lykke; Clausen, Janie Regitse Waël; Ohm, Ragnhild Gaard

    2013-01-01

    This paper describes an efficient tandem sequence for the synthesis of 1,2,3,4-tetrahydro-β-carbolines (THBCs) relying on a ruthenium hydride/Brønsted acid- catalyzed isomerization of allylic amides to N-acyliminium ion intermediates which are trapped by a tethered indolenucleophile. The methodol...... the Suzuki cross-coupling reaction to the isomerization/N-acyliminium cyclization sequence. Finally, diastereo- and enantioselective versions of the title reaction have been examined using substrate control (with dr >15: 1) and asymmetric catalysis (ee up to 57%), respectively...

  2. 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.

  3. A New Mn–Salen Micellar Nanoreactor for Enantioselective Epoxidation of Alkenes in Water

    Directory of Open Access Journals (Sweden)

    Francesco P. Ballistreri

    2018-03-01

    Full Text Available A new chiral Mn–salen catalyst, functionalized with a long aliphatic chain and a choline group, able to act as surfactant catalyst for green epoxidation in water, is here described. This catalyst was employed with a commercial surfactant (CTABr leading to a nanoreactor for the enantioselective epoxidation of some selected alkenes in water, using NaClO as oxidant. This is the first example of a nanoreactor for enantioselective epoxidation of non-functionalized alkenes in water.

  4. Direct enantioselective conjugate addition of carboxylic acids with chiral lithium amides as traceless auxiliaries.

    Science.gov (United States)

    Lu, Ping; Jackson, Jeffrey J; Eickhoff, John A; Zakarian, Armen

    2015-01-21

    Michael addition is a premier synthetic method for carbon-carbon and carbon-heteroatom bond formation. Using chiral dilithium amides as traceless auxiliaries, we report the direct enantioselective Michael addition of carboxylic acids. A free carboxyl group in the product provides versatility for further functionalization, and the chiral reagent can be readily recovered by extraction with aqueous acid. The method has been applied in the enantioselective total synthesis of the purported structure of pulveraven B.

  5. Enantioselective 1,3-dipolar cycloadditions of diazoacetates with electron-deficient olefins.

    Science.gov (United States)

    Sibi, Mukund P; Stanley, Levi M; Soeta, Takahiro

    2007-04-12

    [reaction: see text] A general strategy for highly enantioselective 1,3-dipolar cycloaddition of diazoesters to beta-substituted, alpha-substituted, and alpha,beta-disubstituted alpha,beta-unsaturated pyrazolidinone imides is described. Cycloadditions utilizing less reactive alpha,beta-disubstituted dipolarophiles require elevated reaction temperatures, but still provide the corresponding pyrazolines with excellent enantioselectivities. Finally, an efficient synthesis of (-)-manzacidin A employing this cycloaddition methodology as a key step is illustrated.

  6. Direct Enantioselective Conjugate Addition of Carboxylic Acids with Chiral Lithium Amides as Traceless Auxiliaries

    Science.gov (United States)

    2016-01-01

    Michael addition is a premier synthetic method for carbon–carbon and carbon–heteroatom bond formation. Using chiral dilithium amides as traceless auxiliaries, we report the direct enantioselective Michael addition of carboxylic acids. A free carboxyl group in the product provides versatility for further functionalization, and the chiral reagent can be readily recovered by extraction with aqueous acid. The method has been applied in the enantioselective total synthesis of the purported structure of pulveraven B. PMID:25562717

  7. The synthesis of benzimidazoles and quinoxalines from aromatic diamines and alcohols by iridium-catalyzed acceptorless dehydrogenative alkylation.

    Science.gov (United States)

    Hille, Toni; Irrgang, Torsten; Kempe, Rhett

    2014-05-05

    Benzimidazoles and quinoxalines are important N-heteroaromatics with many applications in pharmaceutical and chemical industry. Here, the synthesis of both classes of compounds starting from aromatic diamines and alcohols (benzimidazoles) or diols (quinoxalines) is reported. The reactions proceed through acceptorless dehydrogenative condensation steps. Water and two equivalents of hydrogen are liberated in the course of the reactions. An Ir complex stabilized by the tridentate P^N^P ligand N(2) ,N(6) -bis(di-isopropylphosphino)pyridine-2,6-diamine revealed the highest catalytic activity for both reactions. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Integrative assessment of enantioselectivity in endocrine disruption and immunotoxicity of synthetic pyrethroids

    Energy Technology Data Exchange (ETDEWEB)

    Zhao Meirong [Research Center of Environmental Science, College of Biological and Environmental Engineering, Zhejiang University of Technology, Hangzhou 310032 (China); Chen Fang [College of Environmental Science and Engineering, Zhejiang Gongshang University, Hangzhou 310018 (China); Wang Cui; Zhang Quan [Research Center of Environmental Science, College of Biological and Environmental Engineering, Zhejiang University of Technology, Hangzhou 310032 (China); Gan Jianying [Department of Environmental Sciences, University of California, Riverside, CA 92521 (United States); Liu Weiping, E-mail: wliu@zjut.edu.c [Research Center of Environmental Science, College of Biological and Environmental Engineering, Zhejiang University of Technology, Hangzhou 310032 (China)

    2010-05-15

    The increasing release of chiral chemicals into the environment dictates attention to a better understanding of enantioselectivity in their human and ecotoxicological effects. Although enantioselectivity has been considered in many recent studies, there is little effort for discerning the connection between different processes, and as such, our current knowledge about chiral contaminants is rather scattered and incoherent. In this study, we simultaneously evaluated enantioselectivity of two chiral pesticides, lambda-cyhalothrin (LCT) and (Z)-cis-bifenthrin (cis-BF), in immunotoxicity to macrophage cells (RAW264.7), and endocrine disruption activity in human breast carcinoma cell line MCF-7. Analysis of cell proliferation, cell viability, apoptosis, and receptor gene expression showed significant differences between the enantiomers of LCT or cis-BF in estrogenic potential and immunocytotoxicity. The selectivity in these effects consistently followed the same direction, with (-)-LCT or 1S-cis-BF displaying a greater activity than its counterpart. The consistency was attributed to interplaying mechanisms in the closely interacting immune and endocrine systems. The underlying interplays suggest that other chiral xenobiotics may also show a directional enantioselectivity in immunotoxicity and endocrine toxicity. Given that many biological processes are inter-related, enantioselectivity may follow specific patterns that can be revealed via integrative assessments as demonstrated in this study. - Chiral contaminants should consider multiple effects and relate directions of enantioselectivity to their interplaying processes.

  9. Integrative assessment of enantioselectivity in endocrine disruption and immunotoxicity of synthetic pyrethroids

    International Nuclear Information System (INIS)

    Zhao Meirong; Chen Fang; Wang Cui; Zhang Quan; Gan Jianying; Liu Weiping

    2010-01-01

    The increasing release of chiral chemicals into the environment dictates attention to a better understanding of enantioselectivity in their human and ecotoxicological effects. Although enantioselectivity has been considered in many recent studies, there is little effort for discerning the connection between different processes, and as such, our current knowledge about chiral contaminants is rather scattered and incoherent. In this study, we simultaneously evaluated enantioselectivity of two chiral pesticides, lambda-cyhalothrin (LCT) and (Z)-cis-bifenthrin (cis-BF), in immunotoxicity to macrophage cells (RAW264.7), and endocrine disruption activity in human breast carcinoma cell line MCF-7. Analysis of cell proliferation, cell viability, apoptosis, and receptor gene expression showed significant differences between the enantiomers of LCT or cis-BF in estrogenic potential and immunocytotoxicity. The selectivity in these effects consistently followed the same direction, with (-)-LCT or 1S-cis-BF displaying a greater activity than its counterpart. The consistency was attributed to interplaying mechanisms in the closely interacting immune and endocrine systems. The underlying interplays suggest that other chiral xenobiotics may also show a directional enantioselectivity in immunotoxicity and endocrine toxicity. Given that many biological processes are inter-related, enantioselectivity may follow specific patterns that can be revealed via integrative assessments as demonstrated in this study. - Chiral contaminants should consider multiple effects and relate directions of enantioselectivity to their interplaying processes.

  10. Catalytic Enantioselective Alkylation of β-Keto Esters with Xanthydrol in the Presence of Chiral Palladium Complex

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Kyu Yeon; Kim, Dae Young [Soonchunhyang Univ., Asan (Korea, Republic of)

    2016-01-15

    Our research interest has been directed toward the development of synthetic methods for the enantioselective construction of stereogenic carbon centers. Recently, we explored the catalytic enantioselective functionalization of active methines in the presence of chiral palladium(II) complexes. In conclusion, we have accomplished the efficient catalytic enantioselective alkylation of β-keto esters 1 with xanthydrol 2 with high yields and excellent enantioselectivity (up to 98% ee). It should be noted that this alkyaltion reaction proceeds well using air- and moisture-stable chiral palladium com- plexes with low loading (1 mol%)

  11. Enantioselective behaviour of tetraconazole during strawberry wine-making process.

    Science.gov (United States)

    Liu, Na; Pan, Xinglu; Zhang, Shuang; Ji, Mingshan; Zhang, Zhihong

    2018-05-01

    The fate of tetraconazole enantiomers in strawberries during wine-making process was studied. The residues were determined by ultra-performance convergence chromatography tandem triple quadrupole mass spectrometry after each process steps. Results indicated that there was significant enantioselective dissipation of tetraconazole enantiomers during the fermentation process. And (-)-tetraconazole degraded faster than (+)-tetraconazole. The half-lives of (-)-tetraconazole and (+)-tetraconazole were 3.12, 3.76 days with washing procedure and 3.18, 4.05 days without washing procedure. The processing factors of strawberry wine samples after each step were generally less than 1. In particular, the processing factors of the fermentation process were the lowest. The results could help facilitate more accurate risk assessments of tetraconazole during wine-making process. © 2018 Wiley Periodicals, Inc.

  12. Enantioselective organo-photocatalysis mediated by atropisomeric thiourea derivatives.

    Science.gov (United States)

    Vallavoju, Nandini; Selvakumar, Sermadurai; Jockusch, Steffen; Sibi, Mukund P; Sivaguru, Jayaraman

    2014-05-26

    Can photocatalysis be performed without electron or energy transfer? To address this, organo-photocatalysts that are based on atropisomeric thioureas and display lower excited-state energies than the reactive substrates have been developed. These photocatalysts were found to be efficient in promoting the [2+2] photocycloaddition of 4-alkenyl-substituted coumarins, which led to the corresponding products with high enantioselectivity (77-96% ee) at low catalyst loading (1-10 mol%). The photocatalytic cycle proceeds by energy sharing via the formation of both static and dynamic complexes (exciplex formation), which is aided by hydrogen bonding. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Enantioselective bioaccumulation of diniconazole in Tenebrio molitor larvae.

    Science.gov (United States)

    Liu, Chen; LV, Xiao Tian; Zhu, Wen Xue; QU, Hao Yang; Gao, Yong Xin; Guo, Bao Yuan; Wang, Hui Li

    2013-12-01

    The enantioselective bioaccumulation of diniconazole in Tenebrio molitor Linne larva was investigated with liquid chromatography tandem mass spectrometry based on the ChiralcelOD-3R[cellulose tri-(3,5-dimethylphenyl carbamate)] column. In this study we documented the effects of dietary supplementation with wheat bran contaminated by racemic diniconazole at two dose levels of 20 mg kg(-1) and 2 mg kg(-1) (dry weight) in Tenebrio molitor. The results showed that both doses of diniconazole were taken up by Tenebrio molitor rapidly in the first few days, the concentrations of R-enantiomer and S-enantiomer at high doses reached the highest level of 0.55 mg kg(-1) and 0.48 mg kg(-1) , respectively, on the 1(st) d, and the concentrations of them obtained a maxima of 0.129 mg kg(-1) and 0.128 mg kg(-1) at low dose, respectively, on the 3(rd) d, which means that the concentration of diniconazole was proportional to the time of achieving the highest accumulated level. It afterwards attained equilibrium after a sharp decline at both 20 mg kg(-1) and 2 mg kg(-1) of diniconazole. The determination results from the feces of Tenebrio molitor demonstrated that the extraction recovery (ER) values of the high dose group were higher than that of the low dose group and the values were all above 1; therefore, it could be inferred that enantiomerization existed in Tenebrio molitor. Additionally, the biota accumulation factor was used to evaluate the bioaccumulation of diniconazole enantiomers, showing that the bioaccumulation of diniconazole in Tenebrio molitor was enantioselective with preferential accumulation of S-enantiomer. © 2013 Wiley Periodicals, Inc.

  14. Study and development of an Iridium-192 seed for use in ophthalmic cancer

    International Nuclear Information System (INIS)

    Mattos, Fabio Rodrigues de

    2013-01-01

    Even ocular tumors are not among the cases with a higher incidence, they affect the population, especially children. The Institute of Energy and Nuclear Research (IPEN-CNEN/SP) in partnership with Escola Paulista de Medicina (UNIFESP), created a project to develop and implement a alternative treatment for ophthalmic cancer that use brachytherapy iridium-192 seeds. The project arose by reason of the Escola Paulista treat many cancer cases within the Unified Health System (SUS) and the research experience of sealed radioactive sources group at IPEN. The methodology was developed from the available infrastructure and the experience of researchers. The prototype seed presents with a core (192-iridium alloy of iridium-platinum) of 3.0 mm long sealed by a capsule of titanium of 0.8 mm outside diameter, 0.05 mm wall thickness and 4,5mm long. This work aims to study and develop a seed of iridium-192 from a platinum-iridium alloy. No study on the fabrication of these seeds was found in available literature. It was created a methodology that involved: characterization of the material used in the core, creation of device for neutron activation irradiation and and seed sealing tests. As a result, proved the feasibility of the method. As a suggestion for future work, studies regarding metrology and dosimetry of these sources and improvement of the methodology should be carried out, for future implementation in national scope. (author)

  15. Development of iridium coated x-ray mirrors for astronomical applications

    Science.gov (United States)

    Döhring, Thorsten; Probst, Anne-Catherine; Emmerich, Florian; Stollenwerk, Manfred; Stehlíková, Veronika; Friedrich, Peter; Damm, Christine

    2017-08-01

    Future space-based X-ray observatories need to be very lightweight for launcher mass constraints. Therefore they will use a reduced mirror thickness, which results in the additional requirement of low coating stress to avoid deformation of the initial precisely shaped mirror substrates. Due to their excellent reflection properties iridium coatings are sometimes applied for grazing incidence mirrors in astronomical X-ray telescopes. At Aschaffenburg University of Applied Sciences the coating of thin iridium films by an RF-magnetron sputtering technique is under development. The work is embedded in collaborations with the Max-Planck-Institute for Extraterrestrial Physics in Germany, the Czech Technical University in Prague, the Osservatorio Astronomico di Brera in Italy, the German Leibniz Institute for Solid State and Materials Research in Dresden, and the French Institute Fresnel. Sputtering with different parameters leads to iridium films with different properties. The current work is focused on the microstructure of the iridium coatings to study the influence of the substrate and of the argon gas pressure on the thin film growing process. Correlations between coating density, surface micro-roughness, the crystalline structure of the iridium layers, and the expected reflectivity of the X-ray mirror as well as coating stress effects are presented and discussed. The final goal of the project is to integrate the produced prototype mirrors into an X-ray telescope module. On a longer timescale measurements of the mirror modules optical performance are planned at the X-ray test facility PANTER.

  16. Iridium containing honeycomb Delafossites by topotactic cation exchange.

    Science.gov (United States)

    Roudebush, John H; Ross, K A; Cava, R J

    2016-06-07

    We report the structure and magnetic properties of two new iridium-based honeycomb Delafossite compounds, Cu3NaIr2O6 and Cu3LiIr2O6, formed by a topotactic cation exchange reaction. The starting materials Na2IrO3 and Li2IrO3, which are based on layers of IrO6 octahedra in a honeycomb lattice separated by layers of alkali ions, are transformed to the title compounds by a topotactic exchange reaction through heating with CuCl below 450 °C; higher temperature reactions cause decomposition. The new compounds display dramatically different magnetic behavior from their parent compounds - Cu3NaIr2O6 has a ferromagnetic like magnetic transition at 10 K, while Cu3LiIr2O6 retains the antiferromagnetic transition temperature of its parent compound but displays significantly stronger dominance of antiferromagnetic coupling between spins. These results reveal that a surprising difference in the magnetic interactions between the magnetic Ir ions has been induced by a change in the non-magnetic interlayer species. A combination of neutron and X-ray powder diffraction is used for the structure refinement of Cu3NaIr2O6 and both compounds are compared to their parent materials.

  17. [New calculation algorithms in brachytherapy for iridium 192 treatments].

    Science.gov (United States)

    Robert, C; Dumas, I; Martinetti, F; Chargari, C; Haie-Meder, C; Lefkopoulos, D

    2018-05-18

    Since 1995, the brachytherapy dosimetry protocols follow the methodology recommended by the Task Group 43. This methodology, which has the advantage of being fast, is based on several approximations that are not always valid in clinical conditions. Model-based dose calculation algorithms have recently emerged in treatment planning stations and are considered as a major evolution by allowing for consideration of the patient's finite dimensions, tissue heterogeneities and the presence of high atomic number materials in applicators. In 2012, a report from the American Association of Physicists in Medicine Radiation Therapy Task Group 186 reviews these models and makes recommendations for their clinical implementation. This review focuses on the use of model-based dose calculation algorithms in the context of iridium 192 treatments. After a description of these algorithms and their clinical implementation, a summary of the main questions raised by these new methods is performed. Considerations regarding the choice of the medium used for the dose specification and the recommended methodology for assigning materials characteristics are especially described. In the last part, recent concrete examples from the literature illustrate the capabilities of these new algorithms on clinical cases. Copyright © 2018 Société française de radiothérapie oncologique (SFRO). Published by Elsevier SAS. All rights reserved.

  18. Chiral Cu(II-catalyzed enantioselective β-borylation of α,β-unsaturated nitriles in water

    Directory of Open Access Journals (Sweden)

    Lei Zhu

    2015-10-01

    Full Text Available The promising performance of copper(II complexes was demonstrated for asymmetric boron conjugate addition to α,β-unsaturated nitriles in water. The catalyst system, which consisted of Cu(OAc2 and a chiral 2,2′-bipyridine ligand, enabled β-borylation and chiral induction in water. Subsequent protonation, which was accelerated in aqueous medium, led to high activity of this asymmetric catalysis. Both solid and liquid substrates were suitable despite being insoluble in water.

  19. Kinetic resolution of α-bromoamides: Experimental and theoretical investigation of highly enantioselective reactions catalyzed by haloalkane dehalogenases

    NARCIS (Netherlands)

    Westerbeek, Alja; Szymanski, Wiktor; Wijma, Hein J.; Marrink, Siewert; Feringa, Ben L.; Janssen, Dick B.

    2011-01-01

    Haloalkane dehalogenases from five sources were heterologously expressed in Escherichia coli, isolated, and tested for their ability to achieve kinetic resolution of racemic alpha-bromoamides, which are important intermediates used in the preparation of bioactive compounds. To explore the substrate

  20. Determination of surface coverage of catalysts : temperature programmed experiments on platinum and iridium sponge catalysts after low temperature ammonia oxidation

    NARCIS (Netherlands)

    van den Broek, A.C.M.; Grondelle, van J.; Santen, van R.A.

    1999-01-01

    The activity of iridium and platinum sponge catalysts was studied in the low temperature gas phase oxidation of ammonia with oxygen. Under the reaction conditions used, iridium was found to be more active and more selective to nitrogen than platinum. Furthermore it was established from activity

  1. A study on the relationship between iridium concentration in hen eggshell and iridium-enriched feed by NAA

    International Nuclear Information System (INIS)

    Yang Gaochuang; Mao Xueying; Wang Jinchun; Lu Yali; Ouyang Hong; Zhang Zhaohui; Chai Zhifang

    2001-01-01

    Four hens were fed by adding ammonium hexachloroiridate into their forage. After two weeks, Ir concentration in three fractions (eggshell, albumen, egg yolk) of their eggs were measured by instrumental neutron activation analysis (INAA). Ir was present in all the three parts of the eggs. Further, the highest concentration of Ir was found in the egg yolk fraction, about 10 times higher than that in the eggshell and albumen. Moreover, the longer the Ir-containing feed was used, the higher the Ir concentration in the egg fractions was. After 4-6 day feeding, the Ir concentration became stable. The experimental results indicated that the Ir concentration was about 2-7 x 10 -10 g/g in the eggshell fraction compared to 5.6 x 10 -7 g/g in feed. Therefore, the ratio from the feed over the eggshell via gastrointestinal pathway was estimated to be about 0.08%. The new result is useful to evaluate the iridium-enriched eggshell fossils of dinosauria and to interpret the origin of the mass extinction of dinosauria at the end of Cretaceous. (author)

  2. A study on the relationship between iridium concentration in hen eggs and the iridium-enriched feed stuff by INAA

    International Nuclear Information System (INIS)

    Yang Gaochuang; Mao Xueying; Lu Yali; Ouyang Hong; Wang Jinchun; Zhang Zhaohui; Chai Zhifang

    2000-01-01

    Several hens were fed by adding ammonium chloroiridate into their forage. After two weeks, the Ir concentration in three fractions (eggshell, albumen, egg yolk) of their eggs were measured by INAA. Ir was found in all of the three parts. However, the highest concentration of Ir was found in the egg yolk fraction, which was about 10 times higher than that in the eggshell and albumen. Moreover, the longer the Ir-containing feed stuff was used, the higher the Ir concentration in the egg fractions was. After 7-8 days feeding, it kept stable. On the other hand, as soon as adding the Ir-containing additives were stopped, the Ir concentration in the egg fractions fell down quickly. The experimental results indicated that the ratio from the feedstuff to the eggshell via gastrointestinal pathway to be about 0.07 percent. The new result might be beneficial to explain the iridium-enriched dinosaur eggshell fossils and to interpret the origin of the mass extinct event of dinosaur occurred at the end of Cretaceous

  3. Development of an Iridium-192 seed for use in ophthalmic brachytherapy

    International Nuclear Information System (INIS)

    Mattos, Fabio R.; Rostelato, Maria Elisa C.M.; Zeituni, Carlos; Moura, Joao A.; Costa, Osvaldo L.; Feher, Anselmo; Moura, Eduardo S.; Souza, Carla D.; Peleias Junior, Fernando S.

    2011-01-01

    The Institute for Energy and Nuclear Research (IPEN), in partnership with the School or Medicine (UNIFESP), created a project that aims to develop and implement an ophthalmic therapeutic treatment for cancer with Iridium-192 seeds. The School of Medicine treats many cancer cases in the SUS (Brazilian Public Health System), and brachytherapy group of IPEN has extensive experience in prototype sources. The seed to be manufactured will perform as follows: a core of Iridium-192 is packaged inside small cylindrical seeds consist of a titanium capsule of 0.8 mm outer diameter, 0.05 mm wall thickness and 4 5 mm in length. The core is an alloy of platinum-iridium (20/80) of 3.0 mm in length and 0.3 mm in diameter. Material analysis, neutron activation and activity measurements were carried out. (author)

  4. Enantioselective radical addition/trapping reactions with alpha,beta-disubstituted unsaturated imides. Synthesis of anti-propionate aldols.

    Science.gov (United States)

    Sibi, Mukund P; Petrovic, Goran; Zimmerman, Jake

    2005-03-02

    This manuscript describes a highly diastereo- and enantioselective intermolecular radical addition/hydrogen atom transfer to alpha,beta-disubstituted enoates. Additionally, we show that anti-propionate aldol-like products can be easily prepared from alpha-methyl-beta-acyloxyenoates in good yields and high diastereo- and enantioselectivities.

  5. Enhancing the muon-catalyzed fusion yield

    International Nuclear Information System (INIS)

    Jones, S.E.

    1987-01-01

    Much has been learned about muon-catalyzed fusion since the last conference on emerging nuclear energy systems. Here the authors consider what they have learned about enhancing the muon-catalyzed fusion energy yield

  6. Enantioselective Cytotoxicity Profile of o,p’-DDT in PC 12 Cells

    Science.gov (United States)

    Zhang, Chunlong; Wen, Yuezhong; Liu, Weiping

    2012-01-01

    Background The continued uses of dichlordiphenyltrichloroethane (DDT) for indoor vector control in some developing countries have recently fueled intensive debates toward the global ban of this persistent legacy contaminant. Current approaches for ecological and health risk assessment has ignored the chiral nature of DDT. In this study by employing an array of cytotoxicity related endpoints, we investigated the enantioselective cytotoxicity of o,p’-DDT. Principal Findings we demonstrated for the first time that R-(−)-o,p’-DDT caused more neuron cell death by inducing more severe oxidative stress, which selectively imbalanced the transcription of stress-related genes (SOD1, SOD2, HSP70) and enzyme (superoxide dismutase and lactate dehydrogenase) activities, and greater cellular apoptosis compared to its enantiomer S-(+)-o,p’-DDT at the level comparable to malaria area exposure (parts per million). We further elucidated enantioselective modes of action using microarray combined with enzyme-linked immunosorbent assay. The enantioselective apoptosis might involve three signaling pathways via caspase 3, tumor protein 53 (p53) and NFkB. Conclusions Based on DDT stereochemistry and results reported for other chiral pesticides, our results pointed to the same directional enantioselectivity of chiral DDT toward mammalian cells. We proposed that risk assessment on DDT should consider the enantiomer ratio and enantioselectivities. PMID:22937105

  7. Interstitial curietherapy with iridium 192 applied to small cancers of the rectum

    International Nuclear Information System (INIS)

    Papillon, J.; Montbarbon, J.F.; Gerard, J.P.

    1975-01-01

    Intracavity irradiation aimed at curing cancers of the rectum mainly calls on contact radiotherapy but also on interstitial curietherapy. Iridium curietherapy has replaced radium-therapy owing to the better homogeneousness of its action and precise method of assay. It uses a 2 pronged fork containing 2 iridium wires which can be very simply placed in position. It is applied on the one hand to the base of the ulcerated tumour, after abrasion by contactotherapy and on the other hand as a method of prophylactic irradiation after exeresis of a malignant or degenerated polyp where the scar is badly adapted to contactotherapy [fr

  8. Assessment of radiation exposure of personnel during clinical application of radioactive iridium

    Energy Technology Data Exchange (ETDEWEB)

    Dworakowski, M; Krystman-Mazgajska, E; Wysopolski, J [Instytut Onkologii, Warsaw (Poland); Centralne Lab. Ochrony Radiologicznej, Warsaw (Poland))

    1975-01-01

    The authors describe the results of measurements of doses and the evaluation of radiation exposure of the personnel of the Department of General Oncology working with application of radioactive iridium for interstitial and superficial treatment of neoplasma. The doses were measured by the photographic method simultaneously at six sites of the body: on the forehead, left side of the chest, 4th fingers of both hands, and on the left and right sides of the trunk at the level of gonads. The authors believe that introduction of iridium in place of radium will improve the conditions of work from the standpoint of protection against radioactivity.

  9. High Strain Rate Testing of Welded DOP-26 Iridium

    Energy Technology Data Exchange (ETDEWEB)

    Schneibel, J. H. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Miller, R. G. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Carmichael, C. A. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Fox, E. E. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Ulrich, G. B. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); George, E. P. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

    2017-08-01

    The iridium alloy DOP-26 is used to produce Clad Vent Set cups that protect the radioactive fuel in radioisotope thermoelectric generators (RTGs) which provide electric power for spacecraft and rovers. In a previous study, the tensile properties of DOP-26 were measured over a wide range of strain rates and temperatures and reported in ORNL/TM-2007/81. While that study established the properties of the base material, the fabrication of the heat sources requires welding, and the mechanical properties of welded DOP-26 have not been extensively characterized in the past. Therefore, this study was undertaken to determine the mechanical properties of DOP-26 specimens containing a transverse weld in the center of their gage sections. Tensile tests were performed at room temperature, 750, 900, and 1090°C and engineering strain rates of 1×10-3 and 10 s-1. Room temperature testing was performed in air, while testing at elevated temperatures was performed in a vacuum better than 1×10-4 Torr. The welded specimens had a significantly higher yield stress, by up to a factor of ~2, than the non-welded base material. The yield stress did not depend on the strain rate except at 1090°C, where it was slightly higher for the faster strain rate. The ultimate tensile stress, on the other hand, was significantly higher for the faster strain rate at temperatures of 750°C and above. At 750°C and above, the specimens deformed at 1×10-3 s-1 showed pronounced necking resulting sometimes in perfect chisel-edge fracture. The specimens deformed at 10 s-1 exhibited this fracture behavior only at the highest test temperature, 1090°C. Fracture occurred usually in the fusion zone of the weld and was, in most cases, primarily intergranular.

  10. Postoperative irradiation of endometrial cancer by iridium afterloading technique

    International Nuclear Information System (INIS)

    Kucera, H.; Weghaupt, K.

    1988-01-01

    From 1981 to 1986 708 patients were operated and postoperativly treated by total hysterectomy, bilateral salpingo-oophorectomy and postoperative vaginal irradiation with high-dose-afterloading (iridium 192). A percutaneous irradiation (cobalt 60) was done in stage I cases only when myometrial infiltration was deep. Highly differentiated tumors with infiltration of the first and second thirth of the myometrium were treated by vaginal irradiation alone. Poorly differentiated tumors with infiltration of the second and third thirth of the myometrium were treated by vaginal and percutaneous irradiation. A group of 125 cases with good prognosis and with postoperative vaginal irradiation alone had the same five-year-survival of 83% as a group of 152 cases with bad prognosis treated by vaginal and percutaneous irrradiation. This result shows clearly the importance of additional irradiation of the pelvis in cases with bad prognosis factors. The incidence of radiation side effect in all 708 cases was: cystitis 4.6%, proctitis 5.2%, vaginal or rectal ulcera 1.4% and fistulas 0.2%. Cases with vaginal irradiation alone and with the optimal intravaginal fraction dose of 700 cGy (twice) had the lowest level of side effects: cystitis 3.8% proctitis 2.1%, vaginal necrosis 0.7%, no further severe complications. None of the patients with postoperative vaginal irradiation alone had a vaginal recurrence. The incidence of recurrences in 708 patients was 1.6%. All recurrence cases in stage I (0.7%) had bad prognosis factors and were treated with vaginal and percutaneous irradiation. (orig./MG) [de

  11. Blue phosphorescent mono-cyclometalated iridium(III) complexes

    Energy Technology Data Exchange (ETDEWEB)

    Ham, Ho Wan; Yang, Yoon A; Kim, Young Sik [Hongik University, Seoul (Korea, Republic of)

    2010-12-15

    New deep blue phosphorescent iridium(III) complexes comprised of one cyclometalate, two phosphines trans to each other and two cis-ancillary ligands, such as Ir(F{sub 2}Meppy)(PPh{sub 2}Me){sub 2}(H)(Cl), Ir(F{sub 2}Meppy)(PPh{sub 2}Me){sub 2}(H)(NCMe){sup +}, and Ir(F{sub 2}Meppy)(PPh{sub 2}Me){sub 2}(H)(CN), [F{sub 2}Meppy = 2-(2', 4'- difluorophenyl)-4-methyl-pyridine] were synthesized and studied to tune the phosphorescence wavelength to the deep blue region and to enhance the luminescence efficiencies. We investigated the strong field effects of ancillary ligands to gain insight into the factors responsible for the emission color change and the different luminescence efficiency. Reducing the molecular weight of the phosphine ligand with PPh{sub 2}Me leads to more efficient deep-blue organic light-emitting devices (OLED) by thermal processing instead of through solution processing. The electron-withdrawing difluoro group substituted on the phenyl ring, the electron-donating methyl group on the pyridyl ring, and the cyano strong field ancillary ligand increased the HOMO-LUMO gap and achieved a hypsochromic shift in the emission color. As a result, the maximum emission spectra of Ir(F{sub 2}Meppy)-(PPh{sub 2}Me){sub 2}(H)(Cl), Ir(F{sub 2}Meppy)(PPh{sub 2}Me){sub 2}(H)(NCMe){sup +}, and Ir(F{sub 2}Meppy)(PPh{sub 2}Me){sub 2-}(H)(CN) were in the ranges of 440.5, 437, 436 nm, respectively.

  12. Blue phosphorescent mono-cyclometalated iridium(III) complexes

    International Nuclear Information System (INIS)

    Ham, Ho Wan; Yang, Yoon A; Kim, Young Sik

    2010-01-01

    New deep blue phosphorescent iridium(III) complexes comprised of one cyclometalate, two phosphines trans to each other and two cis-ancillary ligands, such as Ir(F 2 Meppy)(PPh 2 Me) 2 (H)(Cl), Ir(F 2 Meppy)(PPh 2 Me) 2 (H)(NCMe) + , and Ir(F 2 Meppy)(PPh 2 Me) 2 (H)(CN), [F 2 Meppy = 2-(2', 4'- difluorophenyl)-4-methyl-pyridine] were synthesized and studied to tune the phosphorescence wavelength to the deep blue region and to enhance the luminescence efficiencies. We investigated the strong field effects of ancillary ligands to gain insight into the factors responsible for the emission color change and the different luminescence efficiency. Reducing the molecular weight of the phosphine ligand with PPh 2 Me leads to more efficient deep-blue organic light-emitting devices (OLED) by thermal processing instead of through solution processing. The electron-withdrawing difluoro group substituted on the phenyl ring, the electron-donating methyl group on the pyridyl ring, and the cyano strong field ancillary ligand increased the HOMO-LUMO gap and achieved a hypsochromic shift in the emission color. As a result, the maximum emission spectra of Ir(F 2 Meppy)-(PPh 2 Me) 2 (H)(Cl), Ir(F 2 Meppy)(PPh 2 Me) 2 (H)(NCMe) + , and Ir(F 2 Meppy)(PPh 2 Me) 2- (H)(CN) were in the ranges of 440.5, 437, 436 nm, respectively.

  13. Enantioselective Effect of Flurbiprofen on Lithium Disposition in Rats.

    Science.gov (United States)

    Uwai, Yuichi; Matsumoto, Masashi; Kawasaki, Tatsuya; Nabekura, Tomohiro

    2017-01-01

    Lithium is administered for treating bipolar disorders and is mainly excreted into urine. Nonsteroidal anti-inflammatory drugs inhibit this process. In this study, we examined the enantioselective effect of flurbiprofen on the disposition of lithium in rats. Pharmacokinetic experiments with lithium were performed. Until 60 min after the intravenous administration of lithium chloride at 30 mg/kg as a bolus, 17.8% of lithium injected was recovered into the urine. Its renal clearance was calculated to be 1.62 mL/min/kg. Neither creatinine clearance (Ccr) nor pharmacokinetics of lithium was affected by the simultaneous injection of (R)-flurbiprofen at 20 mg/kg. (S)-flurbiprofen impaired the renal function and interfered with the urinary excretion of lithium. The ratio of renal clearance of lithium to Ccr was decreased by the (S)-enantiomer. This study clarified that the (S)-flurbiprofen but not (R)-flurbiprofen inhibited the renal excretion of lithium in rats. © 2017 S. Karger AG, Basel.

  14. 1,2-Ferrocenediylazaphosphinines 3: a new class of planar chiral ligands for Cu-catalyzed cyclopropanation

    Energy Technology Data Exchange (ETDEWEB)

    Paek, Seung Hwan; Co, Thanh Thien; Lee, Dong Ho; Park, Yu Chul; Kim, Tae Jeong [Kyungpook National Univ., Daegu (Korea, Republic of)

    2002-12-01

    The synthesis and catalytic application of a new class of planar chiral ferrocenes, 1,2-ferrocenediylazaphos-phinines (1 and 2) are described. They are powerful ligands for the copper(I)-catalyzed asymmetric cyclopropanation of a range of alkenes with diazo esters to exhibit an exceptionally high degree of diastereoselectivity ({approx}100%) in favor of trans isomers, regardless the structure of the olefins and the diazo compounds. Comparative studies between 1 and 2 reveal that the former works better in terms of diastereocontrol. In contrast, however, enantioselectivity is low with both 1 and 2 as a whole although, in certain cases with a proper combination of the olefin and the diazo ester, high optical yields (up to 100% ee) can be achieved. Other reaction parameters such as the reaction temperature and the structure of the ligand do exhibit some influence, although infinitesimal, on both chemical and optical yields.

  15. 1,2-Ferrocenediylazaphosphinines 3: a new class of planar chiral ligands for Cu-catalyzed cyclopropanation

    International Nuclear Information System (INIS)

    Paek, Seung Hwan; Co, Thanh Thien; Lee, Dong Ho; Park, Yu Chul; Kim, Tae Jeong

    2002-01-01

    The synthesis and catalytic application of a new class of planar chiral ferrocenes, 1,2-ferrocenediylazaphos-phinines (1 and 2) are described. They are powerful ligands for the copper(I)-catalyzed asymmetric cyclopropanation of a range of alkenes with diazo esters to exhibit an exceptionally high degree of diastereoselectivity (∼100%) in favor of trans isomers, regardless the structure of the olefins and the diazo compounds. Comparative studies between 1 and 2 reveal that the former works better in terms of diastereocontrol. In contrast, however, enantioselectivity is low with both 1 and 2 as a whole although, in certain cases with a proper combination of the olefin and the diazo ester, high optical yields (up to 100% ee) can be achieved. Other reaction parameters such as the reaction temperature and the structure of the ligand do exhibit some influence, although infinitesimal, on both chemical and optical yields

  16. Silica-Supported Catalyst for Enantioselective Arylation of Aldehydes under Batch and Continuous-Flow Conditions.

    Science.gov (United States)

    Watanabe, Satoshi; Nakaya, Naoyuki; Akai, Junichiro; Kanaori, Kenji; Harada, Toshiro

    2018-05-04

    A silica-supported 3-aryl H 8 -BINOL-derived titanium catalyst exhibited high performance in the enantioselective arylation of aromatic aldehydes using Grignard and organolithium reagents not only under batch conditions but also under continuous-flow conditions. Even with a simple pipet reactor packed with the heterogeneous catalyst, the enantioselective production of chiral diarylmethanols could be achieved through a continuous introduction of aldehydes and mixed titanium reagents generated from the organometallic precursors. The pipet reactor could be used repeatedly in different reactions without appreciable deterioration of the activity.

  17. Influence of biochar on the enantioselective behavior of the chiral fungicide metalaxyl in soil

    Science.gov (United States)

    Gámiz, Beatriz; Pignatello, Joseph J.; Hermosín, María Carmen; Cox, Lucía; Celis, Rafael

    2015-04-01

    Chiral pesticides comprise an emerging and important class of organic pollutants currently, accounting for more than a quarter of used pesticides. Consequently, the contamination problems caused by chiral pesticides are concern matter and factors affecting enantioselective processes of chiral pesticides in soil need to be understood. For example, certain soil management practices, such as the use of organic amendments, can affect the enantioselective behavior of chiral pesticides in soils. Recently, biochar (BC), i.e. organic matter subjected to pyrolysis, has been proposed as organic amendment due to beneficial properties such as its high stability against decay in soil environments and its apparent ability to influence the availability of nutrients. BC is considered to be more biologically inert as compared to otherforms of organic carbon. However, its side-effects on the enantioselectivity of processes affecting the fate of chiral pesticides is unknown. The aim of this study was to assess the effect of biochar (BC) on the enantioselectivity of sorption, degradation, and leaching of the chiral fungicide metalaxyl in an agricultural soil. Amending the soil with BC (2% w/w) resulted in 3 times higher sorption of metalaxyl enantiomers compared to unamended soil, but no enantioselectivity in the process was observed. Moreover, both enantiomers showed some resistance to be desorbed in BC-amended soil compared to unamended soil. Dissipation studies revealed that the degradation of metalaxylwas more enantioselective in the unamended soil than in BC-amended soil. In unamended soil, R-metalaxyl(biologically active) and S- metalaxyl had half-lives (t1/2) of 3 and 34 days, respectively. BC enhanced the persistence of both enantiomers in the soil, with R-metalaxyl being degraded faster (t1/2=43 days) than S-metalaxyl (t1/2= 100 days). The leaching of both S-and R-metalaxyl was almost suppressed after amending the soil with BC; less than 10% of the fungicide applied to soil

  18. A pH Sensor Based on a Stainless Steel Electrode Electrodeposited with Iridium Oxide

    Science.gov (United States)

    Martinez, C. C. M.; Madrid, R. E.; Felice, C. J.

    2009-01-01

    A simple procedure to make an iridium oxide (IrO[subscript 2]) electrodeposited pH sensor, that can be used in a chemical, biomedical, or materials laboratory, is presented here. Some exercises, based on this sensor, that can be used to teach important concepts in the field of biomedical, biochemical, tissue, or materials engineering, are also…

  19. Preparation and determination of kerma for Iridium 192 sources of low dose rate for brachytherapy

    International Nuclear Information System (INIS)

    Tendilla, J.I.; Tovar M, V.; Mitsoura, E.; Aguilar H, F.; Alanis M, J.

    2000-01-01

    The practice of Brachytherapy with Iridium-192 sources of low dose rate (0.4 - 0.8 Gy/h) is a technique used in the treatment of diverse illnesses. in this work the preparation, quality control and calibration are presented in terms of kerma in air of Iridium-192 using as target these recycled Iridium-Platinum wires. The targets were obtained as decayed sources of different radio therapeutical centers in the country and they were characterized by Scanning electron microscopy in order to determine their chemical composition. Subsequently it was developed an experimental design to establish the effect of neutron flux, geometrical array and irradiation time over the activity and percentage of the sources homogeneity. The homogeneity was determined by auto radiography and by Gamma spectroscopy. Once the optimal irradiation conditions were established, it is determined the apparent activity and kerma in air using a well type ionization chamber with traceability to a primary laboratory. Iridium-192 sources were obtained with an average homogeneity 96 %, apparent activity 282.129 ± 0.531 M Bq and kerma in air 0.03200 ± 0.00006 m Gy m/h A. (Author)

  20. 76 FR 46313 - Notice of Issuance of Final Determination Concerning Iridium Satellite Telephones

    Science.gov (United States)

    2011-08-02

    ... modulates them into radio streams that communicate with the Iridium gateway network infrastructure using a... (DSP) cores, made in China, and two radio frequency (RF) backend chips, made in Taiwan. The bill of... marking of a cellular phone. CBP found that a digital mobile telephone was substantially transformed in...

  1. Measurements of iridium and the meteoric impact hypothesis at cretaceous end

    International Nuclear Information System (INIS)

    Sircilli Neto, F.

    1986-12-01

    Both instrumental and radiochemical neutron activation analysis methods were developed for trace-element determination, such as iridium and gold, for application in cosmochemistry. The magnitude of the determined concentrations is in the range of parts per billion. In the instrumental method 1.5 grams of sample were submitted to irradiation by 10 13 thermal neutrons.cm -2 .s -1 during 32 hours. The gamma spectrometry is carried out with 10 to 12 hours counting time after 40 days of decay. In the radiochemical analysis a method of radiochemical separation of noble metals based on tellurium coprecipitation is implanted for iridium and gold determinations. As an application of the instrumental neutron activation analysis, preliminary iridium concentrations are measured for the first time in sedimentary rocks collected in the Brazilian territory. These techniques for determinations of iridium will be useful to check the asteroid impact hypothesis, which is supposed to be the cause of the great Cretaceous/Tertiary mass extinction, using samples collected in the South Hemisphere. (Author) [pt

  2. Report of Iridium/{sup 238}PuO{sub 2} Compatibility Test

    Energy Technology Data Exchange (ETDEWEB)

    Taylor, D.H.

    2001-08-09

    This study indicates that the chemical purity of the fuel used presently to fabricate fueled clad vent sets will not present any special problems to the performance of the fueled clad vent sets as intended. However, cation impurities in the fuel can have a deleterious effect on the iridium cladding and vents and should be minimized as much as practical.

  3. Single orientation graphene synthesized on iridium thin films grown by molecular beam epitaxy

    Energy Technology Data Exchange (ETDEWEB)

    Dangwal Pandey, A., E-mail: arti.pandey@desy.de; Grånäs, E.; Shayduk, R.; Noei, H.; Vonk, V. [Deutsches Elektronen-Synchrotron (DESY), D-22607 Hamburg (Germany); Krausert, K.; Franz, D.; Müller, P.; Keller, T. F.; Stierle, A., E-mail: andreas.stierle@desy.de [Deutsches Elektronen-Synchrotron (DESY), D-22607 Hamburg (Germany); Fachbereich Physik, Universität Hamburg, D-22607 Hamburg (Germany)

    2016-08-21

    Heteroepitaxial iridium thin films were deposited on (0001) sapphire substrates by means of molecular beam epitaxy, and subsequently, one monolayer of graphene was synthesized by chemical vapor deposition. The influence of the growth parameters on the quality of the Ir films, as well as of graphene, was investigated systematically by means of low energy electron diffraction, x-ray reflectivity, x-ray diffraction, Auger electron spectroscopy, scanning electron microscopy, and atomic force microscopy. Our study reveals (111) oriented iridium films with high crystalline quality and extremely low surface roughness, on which the formation of large-area epitaxial graphene is achieved. The presence of defects, like dislocations, twins, and 30° rotated domains in the iridium films is also discussed. The coverage of graphene was found to be influenced by the presence of 30° rotated domains in the Ir films. Low iridium deposition rates suppress these rotated domains and an almost complete coverage of graphene was obtained. This synthesis route yields inexpensive, air-stable, and large-area graphene with a well-defined orientation, making it accessible to a wider community of researchers for numerous experiments or applications, including those which use destructive analysis techniques or irreversible processes. Moreover, this approach can be used to tune the structural quality of graphene, allowing a systematic study of the influence of defects in various processes like intercalation below graphene.

  4. Triazole-pyridine ligands: a novel approach to chromophoric iridium arrays

    NARCIS (Netherlands)

    Juríček, M.; Felici, M.; Contreras-Carballada, P.; Lauko, J.; Bou, S.R.; Kouwer, P.H.J.; Brouwer, A.M.; Rowan, A.E.

    2011-01-01

    We describe a novel modular approach to a series of luminescent iridium complexes bearing triazole-pyridine-derived ligands that were conveniently prepared by using "click" chemistry. One, two or three triazole-pyridine units were effectively built into the heteroaromatic macromolecule using

  5. Synthesis and Luminescence Properties of Iridium(III Azide- and Triazole-Bisterpyridine Complexes

    Directory of Open Access Journals (Sweden)

    Timothy W. Schmidt

    2013-07-01

    Full Text Available We describe here the synthesis of azide-functionalised iridium(III bisterpyridines using the “chemistry on the complex” strategy. The resulting azide-complexes are then used in the copper(I-catalysed azide-alkyne Huisgen 1,3-dipolar cycloaddition “click chemistry” reaction to from the corresponding triazole-functionalised iridium(III bisterpyridines. The photophysical characteristics, including lifetimes, of these compounds were also investigated. Interestingly, oxygen appears to have very little effect on the lifetime of these complexes in aqueous solutions. Unexpectedly, sodium ascorbate acid appears to quench the luminescence of triazole-functionalised iridium(III bisterpyridines, but this effect can be reversed by the addition of copper(II sulfate, which is known to oxidize ascorbate under aerobic conditions. The results demonstrate that iridium(III bisterpyridines can be functionalized for use in “click chemistry” facilitating the use of these photophysically interesting complexes in the modification of polymers or surfaces, to highlight just two possible applications.

  6. Mechanistic investigation of the iridium-catalysed alkylation of amines with alcohols

    DEFF Research Database (Denmark)

    Fristrup, Peter; Tursky, Matyas; Madsen, Robert

    2012-01-01

    where the intermediate aldehyde stays coordinated to the iridium catalyst and reacts with the amine to give a hemiaminal which is also bound to the catalyst. Dehydration to the imine and reduction to the product amine also takes place without breaking the coordination to the catalyst. The fact...

  7. The asymmetric rotator model applied to odd-mass iridium isotopes

    International Nuclear Information System (INIS)

    Piepenbring, R.

    1980-04-01

    The method of inversion of the eigenvalue problem previously developed for nuclei with axial symmetry is extended to asymmetric equilibrium shapes. This new approach of the asymmetric rotator model is applied to the odd-mass iridium isotopes. A satisfactory and coherent description of the observed energy spectra is obtained, especially for the lighter isotopes

  8. Electrogenerated chemiluminescence of a cationic cyclometalated iridium complex–Nafion modified electrode in neutral aqueous solution

    International Nuclear Information System (INIS)

    Dong, YongPing; Ni, ZiYue; Zhang, Jing; Tong, BiHai; Chu, XiangFeng

    2013-01-01

    Electrogenerated chemiluminescence (ECL) of a cationic cyclometalated iridium complex, [(pqcm) 2 Ir(bpy)](PF 6 ) (1, pqcmH=2-phenyl-quinoline-4-carboxylic acid methyl ester, bpy=2,2′-bipyridine), was investigated at a bare glassy carbon electrode in CH 3 CN solution and 4 ECL peaks were observed. Then, the ECL of the iridium complex was studied in neutral phosphate buffer solution (PBS) by immobilizing it on a glassy carbon electrode. Two closely located ECL peaks were obtained at 1.07 and 1.40 V when the potential was scanned from −3.00 V to 2.20 V, while only one broad ECL peak located around −2.0 V was obtained when the potential was scanned from 2.20 V to −3.00 V. In the presence of oxalate, one ECL peak located around 1.22 V could be obtained except the broad ECL peak located at −2.00 V. The ECL peak at positive potential range was enhanced more than one magnitude in the presence of Nafion and was nearly 5-times higher than that of Ru(bpy) 3 2+ –Nafion modified electrode, suggesting that the synthesized iridium complex has great application potential in ECL detection. The ECL spectra of iridium complex were identical to its photoluminescence spectrum, indicating the same metal-to-ligand charge transfer (MLCT) excited states. The mechanisms of ECL were proposed based on the experimental results. The present ECL sensor gave a linear response for the oxalate concentration from 1.0×10 −6 to 1.0×10 −4 mol L −1 with a detection limit (S/N=3) of 9.1×10 −7 mol L −1 . -- Graphical abstract: Electrochemiluminescence (ECL) of immobilized novel cationic cyclometalated iridium complex in neutral phosphate buffer solution is reported for the first time. The intensity of iridium complex ECL is 5-times higher than that of Ru(bpy) 3 2+ ECL. Highlights: ► Cationic cyclometalated iridium complex was modified on a bare electrode. ► Electrochemiluminescence (ECL) of the modified electrode was studied. ► The ECL intensity is higher than that of Ru

  9. Production of iridium-192 radiation sources: Indian Experience

    International Nuclear Information System (INIS)

    Sastry, K.V.S.; Kolhe, O.T.; Nagarja, P.S.; Paramr, Y.D.

    2002-01-01

    Board of Radiation and Isotope Technology (BRIT), a unit under the Department of Atomic Energy is fabricating and supplying Ir-192 industrial radiography sources for various models of radiography cameras for use in the industry for non-destructive testing. Basically these sources are fabricated by encapsulating the required quantity of the activity in stainless steel 316 L capsules using Tungsten Inert gas welding process and crimping/attaching to the respective pigtail assemblies of the radiography cameras. The inactive iridium pellets are irradiated in the DHRUVA reactor at a flux on 1.8 X 10 14 n/cm 2 /sec. The performance classification of these source encapsulation for various conditions of normal and accidental nature are tested by subjecting the prototype sources as per the standard laid down by the regulatory authority, Atomic Energy Regulatory Board, in India. The sources are fabricated as per the national and international standards. Activity of the sources varies from 37O GBq (10 Ci ) to 2.96 TBq (80 Ci ) source strength depending on the requirement of the user. The specific activity of the Ir-192 sources supplied is around 7.4 TBq/gm (200 Ci/gm ). Quality control /Assurance for the manufacture of the source begins from the procurement of the raw material and ends with the finished source. Ir- 192 in the form of -0.3 mm diameter (0.1 mm dia wire of Ir-25 % and Pt-75% sheathed in pure platinum of 0.1 mm thick) is being supplied for use in the treatment of cancer of cervix, tongue etc. by brachytherapy. This is supplied in lengths of 50 cm / 100 cm with 37 - 185 GBq/cm ( 1-5 mCi/cm) activity. Annually 925 TBq (25 kCi) of Ir-192 for industrial radiography and about 60 meters of wire for brachytherapy are being fabricated and supplied. Because of the quality of these sources BRIT not only caters to the Indian industry but also is able to export sources to the third world countries. (Author)

  10. Testing of electroformed deposited iridium/powder metallurgy rhenium rockets

    Science.gov (United States)

    Reed, Brian D.; Dickerson, Robert

    1996-01-01

    High-temperature, oxidation-resistant chamber materials offer the thermal margin for high performance and extended lifetimes for radiation-cooled rockets. Rhenium (Re) coated with iridium (Ir) allow hours of operation at 2200 C on Earth-storable propellants. One process for manufacturing Ir/Re rocket chambers is the fabrication of Re substrates by powder metallurgy (PM) and the application of Ir coatings by using electroformed deposition (ED). ED Ir coatings, however, have been found to be porous and poorly adherent. The integrity of ED Ir coatings could be improved by densification after the electroforming process. This report summarizes the testing of two 22-N, ED Ir/PM Re rocket chambers that were subjected to post-deposition treatments in an effort to densify the Ir coating. One chamber was vacuum annealed, while the other chamber was subjected to hot isostatic pressure (HIP). The chambers were tested on gaseous oxygen/gaseous hydrogen propellants, at mixture ratios that simulated the oxidizing environments of Earth-storable propellants. ne annealed ED Ir/PM Re chamber was tested for a total of 24 firings and 4.58 hr at a mixture ratio of 4.2. After only 9 firings, the annealed ED Ir coating began to blister and spall upstream of the throat. The blistering and spalling were similar to what had been experienced with unannealed, as-deposited ED Ir coatings. The HIP ED Ir/PM Re chamber was tested for a total of 91 firings and 11.45 hr at mixture ratios of 3.2 and 4.2. The HIP ED Ir coating remained adherent to the Re substrate throughout testing; there were no visible signs of coating degradation. Metallography revealed, however, thinning of the HIP Ir coating and occasional pores in the Re layer upstream of the throat. Pinholes in the Ir coating may have provided a path for oxidation of the Re substrate at these locations. The HIP ED Ir coating proved to be more effective than vacuum annealed and as-deposited ED Ir. Further densification is still required to

  11. High temperature reactive ion etching of iridium thin films with aluminum mask in CF4/O2/Ar plasma

    Directory of Open Access Journals (Sweden)

    Chia-Pin Yeh

    2016-08-01

    Full Text Available Reactive ion etching (RIE technology for iridium with CF4/O2/Ar gas mixtures and aluminum mask at high temperatures up to 350 °C was developed. The influence of various process parameters such as gas mixing ratio and substrate temperature on the etch rate was studied in order to find optimal process conditions. The surface of the samples after etching was found to be clean under SEM inspection. It was also shown that the etch rate of iridium could be enhanced at higher process temperature and, at the same time, very high etching selectivity between aluminum etching mask and iridium could be achieved.

  12. Antiferromagnetic iridium-manganese intermediate layers for perpendicular recording media (invited)

    Science.gov (United States)

    Srinivasan, Kumar; Piramanayagam, S. N.; Sbiaa, Rachid; Kay, Yew Seng; Tan, Hang Khume; Wong, Seng Kai

    2009-04-01

    Current generation of cobalt-oxide-based perpendicular magnetic recording media uses single or dual ruthenium intermediate layers in order to grow crystallographically textured, and magnetically isolated granular media. In this work, the potential advantages of an antiferromagnetic iridium-manganese intermediate layer directly under the recording layer are highlighted. Owing to its close lattice matching with hexagonal cobalt, iridium-manganese which has the L12, or AuCu3-type crystal structure, can support the heteroepitaxial growth of the cobalt-based recording layer. In one of the media schemes described here, (111) textured iridium-manganese thin film was grown on 7.5 nm thick ruthenium layer. On the iridium-manganese as segregation layer, the Co-oxide-based magnetic recording layer showed perpendicular texture with Δθ50 below 4°, coercivity of over 4000 Oe alongside magnetic exchange decoupling, average grain sizes of 6 nm with distributions under 14%, and improved thermal stability. Measurements of the anisotropy constant did not show any significant change and even an IrMn capping layer was observed to improve the thermal stability. The possible mechanisms through which the IrMn layer could affect the thermal stability are hypothesized. The initial layers of the magnetic recording layer on IrMn segregation layers also showed exchange-decoupled and segregated grains, which is unlike that observed on Ru segregation layers. In a second media scheme, (111) textured iridium-manganese thin film was grown on a crystalline soft magnetic underlayer belonging on top of amorphous soft underlayers. In this scheme, partial pinning of the soft underlayer due to exchange-bias interaction with the IrMn layer was observed. This scheme offers the possibility to reduce the intermediate layer thickness, thus improve media writability, and with further optimization, could potentially facilitate the approach toward 1 Tbits/in.2.

  13. Nanoporous sputtered platinum-iridium-thinfilms for medical and energy applications; Nanoporoese gesputterte Platin-Iridium-Schichten fuer Anwendungen in der Medizin- und Energietechnik

    Energy Technology Data Exchange (ETDEWEB)

    Ganske, Gerald

    2012-10-05

    Sputtering makes it possible to create thinfilms of only a few atom layers and to customize them for special applications by adjusting the deposition parameters. In this work interface-layers are deposited and characterized in biological systems as stimulation electrodes for neural cells and as catalysts in hydrogen fuel cells. First of all, highly porous platinum films were created by sputtering at a pressure of 9 Pa and low power of less than 100 W. These parameters are an ideal compromise between deposition rate, porosity and disordered crystal structure of the layers. Investigations on co-sputtered platinum-iridium-films (PtIr) showed that these films form homogeneous structures and no distinction between the separate layers is possible. It was demonstrated that these films obtain the crystal structure of Pt as well as the finer cauliflower-like structure of iridium, if the atoms reach the substrate surface only with their thermal energy. Furthermore, it was shown that the film composition reflects the sputtering power of the separate targets in a linear way. The structure of the films can be predicted by means of monte-carlo-simulation, which was verified by SEM-pictures. The ratio of the sputtering power can be used to control the amount of interface elements which was confirmed by electrochemical tests. Electrode materials for the stimulation of neural cells need a large electrochemically active surface that allows for an interface between electron and ion conductivity. Test on platinum, iridium and PtIr have shown that the films sputtered at the lowest impact energy do have the largest active surface as well as the largest charge delivery capacity (CDC). Iridium films show the highest CDC (48 mC/cm{sup 2}), followed by platinum-iridium (2 mC/cm{sup 2}, 100 W power at both targets) and pure platinum (16 mC/cm{sup 2}). This can be explained by the large surface area of iridium and its electrochemical activation process. Although PtIr layers also show an

  14. Quinine-Promoted, Enantioselective Boron-Tethered Diels-Alder Reaction by Anomeric Control of Transition State Conformation.

    Science.gov (United States)

    Scholl, Katie; Dillashaw, John; Timpy, Evan; Lam, Yu-Hong; DeRatt, Lindsey; Benton, Tyler R; Powell, Jacqueline P; Houk, Kendall N; Morgan, Jeremy B

    2018-05-01

    Diels-Alder reactions of tethered vinyl-metal species offer the opportunity to fashion highly functionalized diol intermediates for synthesis. We have developed the first enantioselective boron-tethered Diels-Alder reaction using quinine as a chiral promoter. Quinine recovery, enantioselectivity enhancement, and manipulation of the cyclohexene core are also investigated. DFT modeling calculations confirm the role of quinine as a bidentate ligand enhancing reaction rates. The enantioselectivity of the cycloaddition is proposed to originate from a boron-centered anomeric effect.

  15. Lipase Catalyzed Kinetic Resolution of rac-2-(3-Methoxy-4-methylphenyl) propan-1-ol and rac-2-(3-Hydroxy-4-methylphenyl)propyl propanoate for S-(+)-Xanthorrhizol

    International Nuclear Information System (INIS)

    Shafioul, Azam Sharif Mohammed; Cheong, Chan Seong

    2012-01-01

    Xanthorrhizol is a bisabolane type of natural sesquiterpene, the major component of essential oils of Curcuma xanthorrhiza. 2-(3-Methoxy-4-methylphenyl)propan-1-ol and 2-(3-hydroxy-4-methyl phenyl)propan-1-ol could be essential building block for enantioselective synthesis of xanthorrhizol. Enantioselective (c = 53%, E = 80 ± 3) for R-(+)-2-(3-hydroxy-4-methylphenyl) propan-1-ol and (c = 58%, E = 27 ± 1) for R-(+)-2-(3- methoxy-4-methylphenyl) propan-1-ol resolution processes were developed via lipase-catalyzed reaction. We found lipase Aspergillus oryzae (AOL) and Porcine pancreas (PPL) are selective to transesterification and hydrolysis in organic and aqueous phase. Modified demethylated substrate is appropriate for enantioselective hydrolysis reaction without any additives. Enantiopure chiral alcohol was crystallized from ethyl acetate/ n-hexane co-solvent system. Gram scale resolved chiral intermediate will facilitate the synthesis of the unnatural S-(+)-xanthorrhizol, the corresponding isomer of the natural one

  16. Lipase Catalyzed Kinetic Resolution of rac-2-(3-Methoxy-4-methylphenyl) propan-1-ol and rac-2-(3-Hydroxy-4-methylphenyl)propyl propanoate for S-(+)-Xanthorrhizol

    Energy Technology Data Exchange (ETDEWEB)

    Shafioul, Azam Sharif Mohammed [University of Science and Technology, Daejeon (Korea, Republic of); Cheong, Chan Seong [Korea Institute of Science and Technology, Seoul (Korea, Republic of)

    2012-02-15

    Xanthorrhizol is a bisabolane type of natural sesquiterpene, the major component of essential oils of Curcuma xanthorrhiza. 2-(3-Methoxy-4-methylphenyl)propan-1-ol and 2-(3-hydroxy-4-methyl phenyl)propan-1-ol could be essential building block for enantioselective synthesis of xanthorrhizol. Enantioselective (c = 53%, E = 80 ± 3) for R-(+)-2-(3-hydroxy-4-methylphenyl) propan-1-ol and (c = 58%, E = 27 ± 1) for R-(+)-2-(3- methoxy-4-methylphenyl) propan-1-ol resolution processes were developed via lipase-catalyzed reaction. We found lipase Aspergillus oryzae (AOL) and Porcine pancreas (PPL) are selective to transesterification and hydrolysis in organic and aqueous phase. Modified demethylated substrate is appropriate for enantioselective hydrolysis reaction without any additives. Enantiopure chiral alcohol was crystallized from ethyl acetate/ n-hexane co-solvent system. Gram scale resolved chiral intermediate will facilitate the synthesis of the unnatural S-(+)-xanthorrhizol, the corresponding isomer of the natural one.

  17. Enantioselective Synthesis of (-)-Vallesine: Late-Stage C17-Oxidation via Complex Indole Boronation.

    Science.gov (United States)

    Antropow, Alyssa H; Garcia, Nicholas R; White, Kolby L; Movassaghi, Mohammad

    2018-06-04

    The first enantioselective total synthesis of (-)-vallesine via a strategy that features a late-stage regioselective C17-oxidation followed by a highly stereoselective transannular cyclization is reported. The versatility of this approach is highlighted by the divergent synthesis of the archetypal alkaloid of this family, (+)-aspidospermidine, and an A-ring-oxygenated derivative, (+)-deacetylaspidospermine, the precursor to (-)-vallesine, from a common intermediate.

  18. In-silico driven engineering of enantioselectivity of a penicillin G acylase towards active pharmaceutical ingredients

    Czech Academy of Sciences Publication Activity Database

    Grulich, Michal; Brezovský, J.; Štěpánek, Václav; Palyzová, Andrea; Marešová, Helena; Zahradník, Jiří; Kyslíková, Eva; Kyslík, Pavel

    2016-01-01

    Roč. 133, Supplement 1 (2016), s. 53-59 ISSN 1381-1177 Institutional support: RVO:61388971 Keywords : Docking experiments * Enantioselectivity * Penicillin G acylase Subject RIV: EE - Microbiology, Virology OBOR OECD: Microbiology Impact factor: 2.269, year: 2016

  19. Enantioselective polymerization of epoxides using biaryl-linked bimetallic cobalt catalysts: A mechanistic study

    KAUST Repository

    Ahmed, Syud M.; Poater, Albert; Childers, M. Ian; Widger, Peter C B; Lapointe, Anne M.; Lobkovsky, Emil B.; Coates, Geoffrey W.; Cavallo, Luigi

    2013-01-01

    The enantioselective polymerization of propylene oxide (PO) using biaryl-linked bimetallic salen Co catalysts was investigated experimentally and theoretically. Five key aspects of this catalytic system were examined: (1) the structural features of the catalyst, (2) the regio- and stereoselectivity of the chain-growth step, (3) the probable oxidation and electronic state of Co during the polymerization, (4) the role of the cocatalyst, and (5) the mechanism of monomer enchainment. Several important insights were revealed. First, density functional theory (DFT) calculations provided detailed structural information regarding the regio- and stereoselective chain-growth step. Specifically, the absolute stereochemistry of the binaphthol linker determines the enantiomer preference in the polymerization, and the interaction between the salen ligand and the growing polymer chain is a fundamental aspect of enantioselectivity. Second, a new bimetallic catalyst with a conformationally flexible biphenol linker was synthesized and found to enantioselectively polymerize PO, though with lower enantioselectivity than the binaphthol linked catalysts. Third, DFT calculations revealed that the active form of the catalyst has two active exo anionic ligands (chloride or carboxylate) and an endo polymer alkoxide which can ring-open an adjacent cobalt-coordinated epoxide. Fourth, calculations showed that initiation is favored by an endo chloride ligand, while propagation is favored by the presence of two exo carboxylate ligands. © 2013 American Chemical Society.

  20. Aziridino Alcohols as Catalysts for the Enantioselective Addition of Diethylzinc to Aldehydes

    DEFF Research Database (Denmark)

    Tanner, David Ackland; Kornø, Hanne Tøfting; Guijarro, David

    1998-01-01

    The chiral aziridino alcohols 1 -3 have been prepared either from amino acids (1a from serine; 1b - 1i and 3 from threonine; 2a - 2e from allo-threonine) or via asymmetric synthesis (1j, 1k, 1l and 2f from methyl cinnamate). These easily available ligands act as catalysts for the enantioselective...

  1. Enantioselective radical reactions. Evaluation of nitrogen protecting groups in the synthesis of β2-amino acids

    Science.gov (United States)

    Sibi, Mukund P.; Patil, Kalyani

    2006-01-01

    We have investigated the effect of nitrogen protecting groups in radical addition trapping experiments leading to β2-amino acids. Of the three N-protecting groups examined, the phthalimido group was optimal with respect to both yields and enantioselectivity. Additionally, radical additions to more complex acrylates were also investigated, which provided access to functionalized β2-amino acids in modest selectivity. PMID:16799704

  2. Enantioselective radical reactions. Evaluation of nitrogen protecting groups in the synthesis of beta-amino acids.

    Science.gov (United States)

    Sibi, Mukund P; Patil, Kalyani

    2006-02-20

    We have investigated the effect of nitrogen protecting groups in radical addition trapping experiments leading to beta(2)-amino acids. Of the three N-protecting groups examined, the phthalimido group was optimal with respect to both yields and enantioselectivity. Additionally, radical additions to more complex acrylates were also investigated, which provided access to functionalized beta(2)-amino acids in modest selectivity.

  3. An entry to a chiral dihydropyrazole scaffold: enantioselective [3 + 2] cycloaddition of nitrile imines.

    Science.gov (United States)

    Sibi, Mukund P; Stanley, Levi M; Jasperse, Craig P

    2005-06-15

    We have developed a versatile strategy to access dihydropyrazoles in highly enantioenriched form. Dipolar cycloaddition of electron-deficient acceptors and in situ-generated nitrile imines proceeds with high regio- and enantioselectivity using 10 mol % chiral Lewis acid catalyst. A variety of dihydropyrazoles that incorporate functionality for further manipulation have been prepared.

  4. Exploiting the enantioselectivity of Baeyer-Villiger monooxygenases via boron oxidation

    NARCIS (Netherlands)

    Brondani, Patricia B.; Dudek, Hanna; Reis, Joel S.; Fraaije, Marco W.; Andrade, Leandro H.

    2012-01-01

    The enantioselective carbon-boron bond oxidation of several chiral boron-containing compounds by Baeyer-Villiger monooxygenases was evaluated. PAMO and M446G PAMO conveniently oxidized 1-phenylethyl boronate into the corresponding 1-(phenyl)ethanol (ee = 82-91%). Cyclopropyl boronic esters were also

  5. Enantioselective polymerization of epoxides using biaryl-linked bimetallic cobalt catalysts: A mechanistic study

    KAUST Repository

    Ahmed, Syud M.

    2013-12-18

    The enantioselective polymerization of propylene oxide (PO) using biaryl-linked bimetallic salen Co catalysts was investigated experimentally and theoretically. Five key aspects of this catalytic system were examined: (1) the structural features of the catalyst, (2) the regio- and stereoselectivity of the chain-growth step, (3) the probable oxidation and electronic state of Co during the polymerization, (4) the role of the cocatalyst, and (5) the mechanism of monomer enchainment. Several important insights were revealed. First, density functional theory (DFT) calculations provided detailed structural information regarding the regio- and stereoselective chain-growth step. Specifically, the absolute stereochemistry of the binaphthol linker determines the enantiomer preference in the polymerization, and the interaction between the salen ligand and the growing polymer chain is a fundamental aspect of enantioselectivity. Second, a new bimetallic catalyst with a conformationally flexible biphenol linker was synthesized and found to enantioselectively polymerize PO, though with lower enantioselectivity than the binaphthol linked catalysts. Third, DFT calculations revealed that the active form of the catalyst has two active exo anionic ligands (chloride or carboxylate) and an endo polymer alkoxide which can ring-open an adjacent cobalt-coordinated epoxide. Fourth, calculations showed that initiation is favored by an endo chloride ligand, while propagation is favored by the presence of two exo carboxylate ligands. © 2013 American Chemical Society.

  6. Optimisation of the enantioselective biocatalytic hydrolysis of naproxen ethyl ester using ChiroCLEC-CR

    CSIR Research Space (South Africa)

    Brady, D

    2004-03-04

    Full Text Available In a biocatalytic reaction the immobilized lipase ChiroCLEC-CR enantioselectively hydrolysed a naproxen ethyl ester racemate, yielding (S)-naproxen with an enantiomeric excess of more than 98%, an enantiomeric ratio (E) of more than 100...

  7. DNA-based asymmetric catalysis : Sequence-dependent rate acceleration and enantioselectivity

    NARCIS (Netherlands)

    Boersma, Arnold J.; Klijn, Jaap E.; Feringa, Ben L.; Roelfes, Gerard

    2008-01-01

    This study shows that the role of DNA in the DNA-based enantioselective Diels-Alder reaction of azachalcone with cyclopentadiene is not limited to that of a chiral scaffold. DNA in combination with the copper complex of 4,4'-dimethyl-2,2'-bipyridine (Cu-L1) gives rise to a rate acceleration of up to

  8. Equilibrium Studies on Enantioselective Liquid-Liquid Amino Acid Extraction Using a Cinchona Alkaloid Extractant

    NARCIS (Netherlands)

    Schuur, Boelo; Winkelman, Jozef G. M.; Heeres, Hero J.

    2008-01-01

    The enantioselective extraction of aqueous 3,5-dinitrobenzoyl-R,S-leucine (A(R,S)) by a cinchona alkaloid extractant (C) in 1,2-dichloroethane was studied at room temperature (294 K) in a batch system for a range of intake concentrations (10(-4)-10(-3) mol/L) and pH values (3.8-6.6). The

  9. Improvement of enantioselectivity by immobilized imprinting of epoxide hydrolase from Rhodotorula glutinis

    NARCIS (Netherlands)

    Kronenburg, N.A.E.; Bont, de J.A.M.; Fischer, L.

    2001-01-01

    The yeast Rhodotorula glutinis contains an enantioselective, membrane-associated epoxide hydrolase (EH). Partially purified EH was immobilized in a two-step procedure. In the first step, the proteins were derivatized with itaconic anhydride. In the second step, the derivatized proteins were

  10. A DFT exploration of the enantioselective rearrangement of cyclohexene oxide to cyclohexenol

    DEFF Research Database (Denmark)

    Brandt, Peter; Norrby, Per-Ola; Andersson, Pher G.

    2003-01-01

    In this paper, we present computational results for the (1S,3R,4R)-3-(pyrrolidinyl)-methyl-2-azabicyclo[2.2.1]heptane mediated rearrangement of cyclohexene oxide. The results nicely explain the differences in enantioselectivities between catalytic and stoichiometric mode between different ligands...

  11. Efficient and highly enantioselective formation of the all-carbon quaternary stereocentre of lyngbyatoxin A

    DEFF Research Database (Denmark)

    Vital, Paulo J.V.; Tanner, David

    2006-01-01

    Indole 25, an advanced intermediate in a projected enantioselective total synthesis of lyngbyatoxin A 1, was prepared from allylic alcohol 11 in 9 steps and >95% ee, key transformations being the enantiospecific rearrangement of vinyl epoxide 14 and the Hemetsberger-Knittel reaction of azide 24....

  12. Resolution of alpha/beta-amino acids by enantioselective penicillin G acylase from Achromobacter sp

    Czech Academy of Sciences Publication Activity Database

    Grulich, Michal; Brezovský, J.; Štěpánek, Václav; Palyzová, Andrea; Kyslíková, Eva; Kyslík, Pavel

    2015-01-01

    Roč. 122, DEC 2015 (2015), s. 240-247 ISSN 1381-1177 R&D Projects: GA MŠk(CZ) ED1.1.00/02.0109 Institutional support: RVO:61388971 Keywords : Penicillin G acylase * Enantioselectivity * Homologous model Subject RIV: CE - Biochemistry Impact factor: 2.189, year: 2015

  13. Enantioselective analysis of proteinogenic amino acids in cerebrospinal fluid by capillary electrophoresis–mass spectrometry

    NARCIS (Netherlands)

    Prior, Amir; Sánchez-Hernández, Laura; Sastre-Toraño, Javier; Marina, Maria Luisa; de Jong, Gerhardus J.; Somsen, Govert W.

    2016-01-01

    d-Amino acids (AAs) are increasingly being recognized as essential molecules in biological systems. Enantioselective analysis of proteinogenic AAs in biological samples was accomplished by CE–MS employing β-CD as chiral selector and ESI via sheath-liquid (SL) interfacing. Prior to analysis, AAs were

  14. The Enantioselectivity of Odor Sensation: Some Examples for Undergraduate Chemistry Courses

    Science.gov (United States)

    Kraft, Philip; Mannschreck, Albrecht

    2010-01-01

    This article discusses seven chiral odorants that demonstrate the enantioselectivity of odor sensation: carvone, Celery Ketone, camphor, Florhydral, 3-methyl-3-sulfanylhexan-1-ol, muscone, and methyl jasmonate. After a general introduction of the odorant-receptor interaction and the combinatorial code of olfaction, the olfactory properties of the…

  15. Simple Aziridino Alcohols as Chiral Ligands. Enantioselective Additions of Diethylzinc to N-Diphenylphosphinoylimines

    DEFF Research Database (Denmark)

    Tanner, David Ackland; Andersson, Pher G.; Guijarro, David

    1996-01-01

    Simple chiral aziridino alcohols 2-5, easily available from L-serine, L-threonine or L-allo-threonine, have been used as ligands to promote the addition of Et(2)Zn to the diphenylphosphinoylimine 1 (Ar=Ph). Enantioselectivities of up to 94% could be obtained by proper choice of the substituents...

  16. A Green, Enantioselective Synthesis of Warfarin for the Undergraduate Organic Laboratory

    Science.gov (United States)

    Wong, Terence C.; Sultana, Camille M.; Vosburg, David A.

    2010-01-01

    The enantioselective synthesis of drugs is of fundamental importance in the pharmaceutical industry. In this experiment, students synthesize either enantiomer of warfarin, a widely used anticoagulant, in a single step from inexpensive starting materials. Stereoselectivity is induced by a commercial organocatalyst, ("R","R")- or…

  17. Metabolism of styrene in the human liver in vitro: interindividual variation and enantioselectivity

    NARCIS (Netherlands)

    Wenker, M. A.; Kezić, S.; Monster, A. C.; de Wolff, F. A.

    2001-01-01

    1. The interindividual variation and enantioselectivity of the in vitro styrene oxidation by cytochrome P450 have been investigated in 20 human microsomal liver samples. Liver samples were genotyped for the CYP2E1*6 and CYP2E1*5B alleles. 2. Kinetic analysis indicated the presence of at least two

  18. A mitochondrial targeted two-photon iridium(III) phosphorescent probe for selective detection of hypochlorite in live cells and in vivo.

    Science.gov (United States)

    Li, Guanying; Lin, Qian; Sun, Lingli; Feng, Changsheng; Zhang, Pingyu; Yu, Bole; Chen, Yu; Wen, Ya; Wang, Hui; Ji, Liangnian; Chao, Hui

    2015-01-01

    Endogenous hypochlorite ion (ClO(-)) is a highly reactive oxygen species (ROS) that is produced from hydrogen peroxide and chloride ions catalyzed by myeloperoxidase (MPO). And mitochondrion is one of the major sources of ROS including ClO(-). In the present work, a two-photon phosphorescent probe for ClO(-) in mitochondria was developed. An iridium(III) complex bearing a diaminomaleonitrile group as ClO(-) reactive moiety specifically responded to ClO(-) over other ions and ROSs. When the probe was reacted with ClO(-) to form an oxidized carboxylate product, a significant enhancement in phosphorescence intensity was observed under one-photon (402 nm) and two-photon (750 nm) excitation, with a two-photon absorption cross-section of 78.1 GM at 750 nm. More importantly, ICP-MS results and cellular images co-stained with Mito-tracker Green demonstrated that this probe possessed high specificity for mitochondria. This probe was applied in the one- and two-photon imaging of ClO(-) in vitro and in vivo. The results suggested endotoxin lipopolysaccharide (LPS) induced ClO(-) mostly generated in the liver of zebrafish. Copyright © 2015 Elsevier Ltd. All rights reserved.

  19. Thermodynamics of Enzyme-Catalyzed Reactions Database

    Science.gov (United States)

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

  20. An Analysis of the FY-1C, Iridium 33, and Cosmos 2251 Fragments

    Science.gov (United States)

    Liou, J.-C.

    2014-01-01

    The beginning of the year 2013 marks the sixth anniversary of the destruction of the Fengyun-1C (FY-1C) weather satellite as the result of an anti-satellite test conducted by China in January 2007 and the fourth anniversary of the accidental collision between Cosmos 2251 and the operational Iridium 33 in February 2009. These two events represent the worst satellite breakups in history. A total of 5579 fragments have been cataloged by the U.S. Space Surveillance Network (SSN), and almost 5000 of them were still in orbit in January 2013. In addition to these cataloged objects, hundreds of thousands (or more) of fragments down to the millimeter size regime were also generated during the breakups. These fragments are too small to be tracked by the SSN, but are large enough to be a safety concern for human space activities and robotic missions in low Earth orbit (LEO, the region below 2000 km altitude). Like their cataloged siblings, many of them remain in orbit today. These two breakup events dramatically changed the landscape of the orbital debris environment in LEO. The spatial density of the cataloged population in January 2013 is shown as the top blue curve. The combined FY-1C, Iridium 33, and Cosmos 2251 fragments (black curve) account for about 50 percent of the cataloged population below an altitude of 1000 km. They are also responsible for the concentrations at 770 km and 850 km, altitudes at which the collisions occurred. The effects of the FY-1C, Iridium 33, and Cosmos 2251 fragments will continue to be felt for decades to come. For example, approximately half of the generated FY-1C fragments will remain in orbit 20 years from now. In general, the Iridium 33 and Cosmos 2251 fragments will decay faster than the FY-1C fragments because of their lower altitudes. Of the Iridium 33 and Cosmos 2251 fragments, the former have much shorter orbital lifetimes than the latter, because lightweight composite materials were heavily used in the construction of the Iridium

  1. Ammonia and hydrazine. Transition-metal-catalyzed hydroamination and metal-free catalyzed functionalization

    Energy Technology Data Exchange (ETDEWEB)

    Bertrand, Guy [Univ. of California, San Diego, CA (United States)

    2012-06-29

    high temperatures and long reaction times. To address this issue, we have developed several new families of carbon- and boron-based ligands, which are even better donors. The corresponding metal complexes (particularly gold, rhodium, iridium, and ruthenium) of all these species will be tested in the Markovnikov and anti-Markovnikov hydroamination of alkynes, allenes, and also alkenes with ammonia and hydrazine. We will also develop metal-free catalytic processes for the functionalization of ammonia and hydrazine. By possessing both a lone pair of electrons and an accessible vacant orbital, singlet carbenes resemble and can mimic the chemical behavior of transition metals. Our preliminary results demonstrate that specially designed carbenes can split the N–H bond of ammonia by an initial nucleophilic activation that prevents the formation of Lewis acid-base adducts, which is the major hurdle for the transition metal catalyzed functionalization of NH3. The use of purely organic compounds as catalysts will eliminate the major drawbacks of transition-metal-catalysis technology, which are the excessive cost of metal complexes (metal + ligands) and in many cases the toxicity of the metal.

  2. Crystallization and preliminary X-ray analysis of an enantioselective halohydrin dehalogenase from Agrobacterium radiobacter AD1

    NARCIS (Netherlands)

    Jong, René M. de; Rozeboom, Henriëtte J.; Kalk, Kor H.; Tang, Lixia; Janssen, Dick B.; Dijkstra, Bauke W.

    2002-01-01

    Halohydrin dehalogenases are key enzymes in the bacterial degradation of vicinal halopropanols and structurally related nematocides. Crystals of the enantioselective halohydrin dehalogenase HheC from Agrobacterium radiobacter AD1 have been obtained at room temperature from hanging-drop

  3. Crystallization and preliminary X-ray analysis of an enantioselective halohydrin dehalogenase from Agrobacterium radiobacter AD1

    NARCIS (Netherlands)

    de Jong, RM; Rozeboom, HJ; Kalk, KH; Tang, Lixia; Janssen, DB; Dijkstra, BW

    Halohydrin dehalogenases are key enzymes in the bacterial degradation of vicinal halopropanols and structurally related nematocides. Crystals of the enantioselective halohydrin dehalogenase HheC from Agrobacterium radiobacter AD1 have been obtained at room temperature from hanging-drop

  4. Total syntheses of mitragynine, paynantheine and speciogynine via an enantioselective thiourea-catalysed Pictet-Spengler reaction

    NARCIS (Netherlands)

    Kerschgens, I. P.; Claveau, E.; Wanner, M.J.; Ingemann, S.; van Maarseveen, J.H.; Hiemstra, H.

    2012-01-01

    The pharmacologically interesting indole alkaloids (-)-mitragynine, (+)-paynantheine and (+)-speciogynine were synthesised in nine steps from 4-methoxytryptamine by a route featuring (i) an enantioselective thiourea-catalysed Pictet-Spengler reaction, providing the tetrahydro-β-carboline ring and

  5. One pot 'click' reactions : tandem enantioselective biocatalytic epoxide ring opening and [3+2] azide alkyne cycloaddition

    NARCIS (Netherlands)

    Campbell-Verduyn, Lachlan S.; Szymanski, Wiktor; Postema, Christiaan P.; Dierckx, Rudi A.; Elsinga, Philip H.; Janssen, Dick B.; Feringa, Ben L.

    2010-01-01

    Halohydrin dehalogenase (HheC) can perform enantioselective azidolysis of aromatic epoxides to 1,2-azido alcohols which are subsequently ligated to alkynes producing chiral hydroxy triazoles in a one-pot procedure with excellent enantiomeric excess.

  6. Tuning and Switching Enantioselectivity of Asymmetric Carboligation in an Enzyme through Mutational Analysis of a Single Hot Spot.

    Science.gov (United States)

    Wechsler, Cindy; Meyer, Danilo; Loschonsky, Sabrina; Funk, Lisa-Marie; Neumann, Piotr; Ficner, Ralf; Brodhun, Florian; Müller, Michael; Tittmann, Kai

    2015-12-01

    Enantioselective bond making and breaking is a hallmark of enzyme action, yet switching the enantioselectivity of the reaction is a difficult undertaking, and typically requires extensive screening of mutant libraries and multiple mutations. Here, we demonstrate that mutational diversification of a single catalytic hot spot in the enzyme pyruvate decarboxylase gives access to both enantiomers of acyloins acetoin and phenylacetylcarbinol, important pharmaceutical precursors, in the case of acetoin even starting from the unselective wild-type protein. Protein crystallography was used to rationalize these findings and to propose a mechanistic model of how enantioselectivity is controlled. In a broader context, our studies highlight the efficiency of mechanism-inspired and structure-guided rational protein design for enhancing and switching enantioselectivity of enzymatic reactions, by systematically exploring the biocatalytic potential of a single hot spot. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. L-Threonine-derived novel bifunctional phosphine-sulfonamide catalyst-promoted enantioselective aza-morita-Baylis-Hillman reaction

    KAUST Repository

    Zhong, Fangrui

    2011-03-18

    A series of novel bifunctional phosphine-sulfonamide organic catalysts were designed and readily prepared from natural amino acids, and they were utilized to promote enantioselective aza-Morita-Baylis-Hillman (MBH) reactions. l-Threonine-derived phosphine-sulfonamide 9b was found to be the most efficient catalyst, affording the desired aza-MBH adducts in high yields and with excellent enantioselectivities. © 2011 American Chemical Society.

  8. Enantioselective Construction of 3-Hydroxypiperidine Scaffolds by Sequential Action of Light and Rhodium upon N-Allylglyoxylamides.

    Science.gov (United States)

    Ishida, Naoki; Nečas, David; Masuda, Yusuke; Murakami, Masahiro

    2015-06-15

    3-Hydroxypiperidine scaffolds were enantioselectively constructed in an atom-economical way by sequential action of light and rhodium upon N-allylglyoxylamides. In a formal sense, the allylic C-H bond was selectively cleaved and enantioselectively added across the ketonic carbonyl group with migration of the double bond (carbonyl-ene-type reaction). © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Enantioselective silver nanoclusters: Preparation, characterization and photoluminescence spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Farrag, Mostafa, E-mail: mostafafarrag@aun.edu.eg

    2016-09-01

    prepared silver nanoclusters were investigated using nitrogen adsorption-desorption at −196 °C. Specific surface area S{sub BET}, pore volume and average pore diameter were calculated. - Highlights: • New wet chemistry method to prepare mirror image small silver clusters protected by penicillamine. • Preparation enantioselective catalysts by easy wet chemistry method. • The synthesized silver clusters have photoluminescence properties. • The synthesized silver clusters show high Anisotropy factors up to 3 × 10{sup −4}. • The adsorption isotherms of all synthesized clusters are mainly of type II of Brunaue’s classification.

  10. Implantation of the maxillary antrum for delivery of iridium brachytherapy and microwave induced hyperthermia

    International Nuclear Information System (INIS)

    Coughlin, C.T.; Wong, T.Z.; Geurkink, N.

    1985-01-01

    A 63 year-old male was referred tp Dartmouth in March 1984 for a locally advanced recurrent squamous cell carcinoma of the left maxillary antrum. This had been initially diagnosed in January 1983 by a Caldwell-Luc procedure and had failed partial resection, external radiation therapy, and multiagent chemotherapy. Our initial evaluation revealed disease replacing the left maxillary antrum, extending into the pterygomaxillary fossa, the lateral aspect of the superior alveloar ridge, and into the soft palate. He was taken to the operating room and under general anesthesia was implanted the 7 catheters through this tumor volume. Two days later a therapeutic (>42 0 C for 1 hour) hyperthermia treatment was administered followed by iridium placement. A second heating was performed upon removal of the iridium and was accomplished without major side effects. Thermometry data and follow-up are presented

  11. Intercalating cobalt between graphene and iridium (111): Spatially dependent kinetics from the edges

    Science.gov (United States)

    Vlaic, Sergio; Rougemaille, Nicolas; Kimouche, Amina; Burgos, Benito Santos; Locatelli, Andrea; Coraux, Johann

    2017-10-01

    Using low-energy electron microscopy, we image in real time the intercalation of a cobalt monolayer between graphene and the (111) surface of iridium. Our measurements reveal that the edges of a graphene flake represent an energy barrier to intercalation. Based on a simple description of the growth kinetics, we estimate this energy barrier and find small, but substantial, local variations. These local variations suggest a possible influence of the graphene orientation with respect to its substrate and of the graphene edge termination on the energy value of the barrier height. Besides, our measurements show that intercalated cobalt is energetically more favorable than cobalt on bare iridium, indicating a surfactant role of graphene.

  12. Surface studies of iridium-alloy grain boundaries associated with weld cracking

    International Nuclear Information System (INIS)

    Mosley, W.C.

    1982-01-01

    Plutonium-238 oxide fuel pellets for the General Purpose Heat Source (GPHS) Radioisotopic Thermoelectric Generators to be used on the NASA Galileo Mission to Jupiter and the International Solar Polar Mission are produced and encapsulated in iridium alloy at the Savannah River Plant (SRP). Underbead cracks occasionally occur in the girth weld on the iridium-alloy-clad vent sets in the region where the gas tungsten arc is quenched. Grain-boundary structures and compositions were characterized by scanning electron microscopy/x-ray energy spectroscopy, electron microprobe analysis and scanning Auger microprobe analysis to determine the cause of weld quench area cracking. Results suggest that weld quench area cracking may be caused by gas porosity or liquation in the grain boundaries

  13. Phosphorescent Organic Light-Emitting Devices: Working Principle and Iridium Based Emitter Materials

    Directory of Open Access Journals (Sweden)

    Emil J. W. List

    2008-08-01

    Full Text Available Even though organic light-emitting device (OLED technology has evolved to a point where it is now an important competitor to liquid crystal displays (LCDs, further scientific efforts devoted to the design, engineering and fabrication of OLEDs are required for complete commercialization of this technology. Along these lines, the present work reviews the essentials of OLED technology putting special focus on the general working principle of single and multilayer OLEDs, fluorescent and phosphorescent emitter materials as well as transfer processes in host materials doped with phosphorescent dyes. Moreover, as a prototypical example of phosphorescent emitter materials, a brief discussion of homo- and heteroleptic iridium(III complexes is enclosed concentrating on their synthesis, photophysical properties and approaches for realizing iridium based phosphorescent polymers.

  14. Extrahepatic bile duct carcinoma treated by intraluminal irradiation with iridium-192 wire. Report of a case

    Energy Technology Data Exchange (ETDEWEB)

    Ikeda, H; Kuroda, T; Uchida, H [Osaka Univ. (Japan). Faculty of Medicine

    1980-08-01

    A 57-year-old male with obstructive jaundice was diagnosed extrahepatic bile duct carcinoma at bifurcation by percutaneous transhepatic cholangiography (PTC). He was treated 3,300 rad of external irradiation and then intraluminal irradiation using the Iridium-192 wire by two times with the aid of PTC internal drainage, each was given by the dose of 1,600 rad at 5 mm inside the tumor from the PTC-tube. He had been well for about 1 year and then died because of ascites and cachexia. Autopsy revealed only microscopic tumor cells remaining around the common duct below the cystic junction. It was confirmed that intraluminal irradiation using the Iridium-192 wire was potentially curable and easily applicable to the bile duct carcinoma.

  15. Extrahepatic bile duct carcinoma treated by intraluminal irradiation with iridium-192 wire

    International Nuclear Information System (INIS)

    Ikeda, Hiro; Kuroda, Tomosumi; Uchida, Hideo

    1980-01-01

    A 57-year-old male with obstructive jaundice was diagnosed extrahepatic bile duct carcinoma at bifurcation by percutaneous transhepatic cholangiography (PTC). He was treated 3,300 rad of external irradiation and then intraluminal irradiation using the Iridium-192 wire by two times with the aid of PTC internal drainage, each was given by the dose of 1,600 rad at 5 mm inside the tumor from the PTC-tube. He had been well for about 1 year and then died because of ascites and cachexia. Autopsy revealed only microscopic tumor cells remaining around the common duct below the cystic junction. It was confirmed that intraluminal irradiation using the Iridium-192 wire was potentially curable and easily applicable to the bile duct carcinoma. (author)

  16. Research of remote control for Chinese Antarctica Telescope based on iridium satellite communication

    Science.gov (United States)

    Xu, Lingzhe; Yang, Shihai

    2010-07-01

    Astronomers are ever dreaming of sites with best seeing on the Earth surface for celestial observation, and the Antarctica is one of a few such sites only left owing to the global air pollution. However, Antarctica region is largely unaccessible for human being due to lacking of fundamental living conditions, travel facilities and effective ways of communication. Worst of all, the popular internet source as a general way of communication scarcely exists there. Facing such a dilemma and as a solution remote control and data transmission for telescopes through iridium satellite communication has been put forward for the Chinese network Antarctic Schmidt Telescopes 3 (AST3), which is currently under all round research and development. This paper presents iridium satellite-based remote control application adapted to telescope control. The pioneer work in China involves hardware and software configuration utilizing techniques for reliable and secure communication, which is outlined in the paper too.

  17. Grain Growth and Precipitation Behavior of Iridium Alloy DOP-26 During Long Term Aging

    Energy Technology Data Exchange (ETDEWEB)

    Pierce, Dean T. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Muralidharan, Govindarajan [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Fox, Ethan E. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Cox, Victoria A. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Geer, Tom [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

    2017-05-01

    The influence of long term aging on grain growth and precipitate sizes and spatial distribution in iridium alloy DOP-26 was studied. Samples of DOP-26 were fabricated using the new process, recrystallized for 1 hour (h) at 1375 C, then aged at either 1300, 1400, or 1500 C for times ranging from 50 to 10,000 h. Grain size measurements (vertical and horizontal mean linear intercept and horizontal and vertical projection) and analyses of iridium-thorium precipitates (size and spacing) were made on the longitudinal, transverse, and rolling surfaces of the as-recrystallized and aged specimens from which the two-dimensional spatial distribution and mean sizes of the precipitates were obtained. The results obtained from this study are intended to provide input to grain growth models.

  18. Electro-catalytic oxidation of ethanol on platinum-iridium mixtures supported on glassy carbon

    International Nuclear Information System (INIS)

    Rodriguez, Henry; Hoyos Bibian

    2004-01-01

    Electro-catalytic oxidation of ethanol on platinum-iridium mixtures supported on glassy carbon was studied, in acid media at different temperatures and concentrations. During the maturation time of deposited iridium, the surface is covered by an irreversible oxide formation, which affects the behavior of the catalytic mixture. The Pt 7 0 Ir 3 0 and Pt 9 0 Ir 1 0 mixtures seem to be a little more active than the Pt/C electrode at potentials below 800 mV (vs. HRE). In all electrodes appears two reactions: partial ethanol oxidation to produce acetaldehyde (main path of reaction at low temperatures and high electrode coverage with ethanol adsorption residues) and the total oxidation to carbon dioxide which is considerable at potential above 800 mV and it is increased with increasing temperature

  19. Interaction of an iridium-clad RTG heat source unit with a simulated terrestrial environment

    International Nuclear Information System (INIS)

    Patterson, J.H.; Herrera, B.; Nelson, G.B.; Matlack, G.M.; Waterbury, G.R.

    1976-02-01

    An iridium-clad, 100-W 238 PuO 2 sphere, a prototype for the multihundred-watt radioisotope thermoelectric generator, was exposed for 1 y to a simulated temperate humid climate in an environmental test chamber containing sandy soil. The hot sphere sank into the soil after the first rain, then gradually acquired a hard crust around it as a result of the rainwater reacting with the hot soil during successive rains. Time and temperature profiles of the sphere were recorded during the weekly rains, and the air and rainwater that percolated through the soil were monitored for plutonium. No plutonium was released from the sphere. Aside from the crust formation, very little reaction occurred between the hot iridium shell and the soil

  20. Rh-catalyzed linear hydroformylation of styrene

    NARCIS (Netherlands)

    Boymans, E.H.; Janssen, M.C.C.; Mueller, C.; Lutz, M.; Vogt, D.

    2012-01-01

    Usually the Rh-catalyzed hydroformylation of styrene predominantly yields the branched, chiral aldehyde. An inversion of regioselectivity can be achieved using strong p-acceptor ligands. Binaphthol-based diphosphite and bis(dipyrrolyl-phosphorodiamidite) ligands were applied in the Rh-catalyzed

  1. An iridium abundance anomaly at the palynological Cretaceous-Tertiary boundary in northern New Mexico

    Science.gov (United States)

    Orth, C.J.; Gilmore, J.S.; Knight, J.D.; Pillmore, C.L.; Tschudy, R.H.; Fassett, J.E.

    1981-01-01

    An iridium abundance anomaly, with concentrations up to 5000 parts per trillion over a background level of 4 to 20 parts per trillion, has been located in sedimentary rocks laid down under freshwater swamp conditions in the Raton Basin of northeastern New Mexico. The anomaly occurs at the base of a coal bed, at the same stratigraphic position at which several well-known species of Cretaceous-age pollen became extinct. Copyright ?? 1981 AAAS.

  2. Substrate-induced antiferromagnetism of ultrathin iron overlayers on the iridium and rhodium (001) surfaces

    Czech Academy of Sciences Publication Activity Database

    Máca, František; Kudrnovský, Josef; Drchal, Václav; Turek, Ilja; Bengone, O.; Redinger, J.

    2009-01-01

    Roč. 11, - (2009), s. 38-40 ISSN 1642-6037 R&D Projects: GA ČR GA202/07/0456; GA MŠk OC09028 Institutional research plan: CEZ:AV0Z10100520; CEZ:AV0Z20410507 Keywords : iridium * rhodium * iron * magnetismus in thin layers * density functional calculations Subject RIV: BM - Solid Matter Physics ; Magnetism

  3. Ammonia synthesis in the presence of rhodium-ruthenium-iridium carbonyl clusters

    International Nuclear Information System (INIS)

    Fedoseev, I.V.; Solov'ev, N.V.

    2007-01-01

    Researches in the field of platinum metal coordination compounds, where nitrogen enters as a ligand in coordination sphere of metal, are discussed. Results of experiments on the ammonia synthesis during the CO+N 2 mixture passing through alkali solution containing mixture of carbonyl clusters of rhodium, ruthenium and iridium at atmospheric pressure are given. Technique of the experiment and steps of assumed reactions of nitrogen fixation by Rh, Ir and Ru carbonyl clusters are demonstrated [ru

  4. Transformation of a Cp*-iridium(III) precatalyst for water oxidation when exposed to oxidative stress.

    Science.gov (United States)

    Zuccaccia, Cristiano; Bellachioma, Gianfranco; Bortolini, Olga; Bucci, Alberto; Savini, Arianna; Macchioni, Alceo

    2014-03-17

    The reaction of [Cp*Ir(bzpy)NO3 ] (1; bzpy=2-benzoylpyridine, Cp*=pentamethylcyclopentadienyl anion), a competent water-oxidation catalyst, with several oxidants (H2 O2 , NaIO4 , cerium ammonium nitrate (CAN)) was studied to intercept and characterize possible intermediates of the oxidative transformation. NMR spectroscopy and ESI-MS techniques provided evidence for the formation of many species that all had the intact Ir-bzpy moiety and a gradually more oxidized Cp* ligand. Initially, an oxygen atom is trapped in between two carbon atoms of Cp* and iridium, which gives an oxygen-Ir coordinated epoxide, whereas the remaining three carbon atoms of Cp* are involved in a η(3) interaction with iridium (2 a). Formal addition of H2 O to 2 a or H2 O2 to 1 leads to 2 b, in which a double MeCOH functionalization of Cp* is present with one MeCOH engaged in an interaction with iridium. The structure of 2 b was unambiguously determined in the solid state and in solution by X-ray single-crystal diffractometry and advanced NMR spectroscopic techniques, respectively. Further oxidation led to the opening of Cp* and transformation of the diol into a diketone with one carbonyl coordinated at the metal (2 c). A η(3) interaction between the three non-oxygenated carbons of "ex-Cp*" and iridium is also present in both 2 b and 2 c. Isolated 2 b and mixtures of 2 a-c species were tested in water-oxidation catalysis by using CAN as sacrificial oxidant. They showed substantially the same activity than 1 (turnover frequency values ranged from 9 to 14 min(-1) ). © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Neutron activation determination of iridium, gold, platinum, and silver in geologic samples

    International Nuclear Information System (INIS)

    Millard, H.T.

    1986-01-01

    Low-level methods for the determination of iridium and other noble metals have been important in recent years due to interest in locating abundance anomalies associated with the Cretaceous/Tertiary (K/T) boundary. Typical iridium anomalies are in the range of 1 to 100 ppb. Thus methods with detection limits near 0.1 ppb should be adequate to detect K/T boundary anomalies. Radiochemical neutron activation analysis methods continue to be required although instrumental neutron activation analysis techniques employing elaborate gamma-counters are under development. In the procedure employed in this study samples irradiated in the epithermal neutron facility of the U.S. Geological Survey TRIGA Reactor are treated with a mini-fire assay technique. The iridium, gold, and silver are collected in a 1-gram metallic lead button. Primary contaminants at this stage are arsenic and antimony. These can be removed by heating the button with a mixture of sodium peroxide and sodium hydroxide. The resulting 0.2-gram lead bead is counted in a Compton suppression spectrometer. Carrier yields are determined by reirradiation of the lead beads. This procedure has been applied to the U.S.G.S. Standard Rock PCC-1. and samples from K/T boundary sites in the Western Interior of North America. (author)

  6. Production of iridium-alloy clad vent sets for the Cassini mission to Saturn

    International Nuclear Information System (INIS)

    Helle, K.J.; Moore, J.P.

    1995-01-01

    Martin Marietta Energy Systems, Inc., has successfully produced the iridium-alloy clad vent sets required for encapsulation of plutonia for the National Aeronautics and Space Administration Cassini mission to Saturn. Numerous improvements were made to the manufacturing process in various areas including dye-penetrant examination of cups, foil part stamping, chemical analysis, tungsten fixturing for laser welding, and enhanced inspections at high magnification. In addition, systems were initiated to ensure process control, and a detailed quality and technical surveillance program was prepared and followed to detect any incipient production problem early in the process so that corrective action could be taken immediately. The quality of the resulting iridium components has been high, and production yields have been above 90%. During the course of the production campaign for the Cassini mission, worker efficiencies lowered production costs, and further cost reductions are possible if operations are consolidated into a single area and bare-forming of the iridium alloys cups can be qualified for flight-quality clad vent sets

  7. Development and characterisation of iridium-192 seeds for brachytherapy treatment of ocular tumors

    International Nuclear Information System (INIS)

    Peleias Jr, F.S.; Zeituni, C.A.; Souza, C.D.; Rostelato, M.E.CM.; Mattos, F.R.; Banega, M.A.G.; Rodrigues, B.T.; Tiezzi, R.; Oliveira, T.B.; Feher, A.; Moura, J.A.; Costa, O.L.

    2014-01-01

    Even ocular tumors are not amongst the cases with a high incidence, they affect the population, particularly children. The Institute of Energy and Nuclear Research (IPEN-CNEN/SP) in partnership with Escola Paulista de Medicina (UNIFESP), created a project to develop an alternative treatment for ophthalmic cancer that uses iridium-192 seeds in brachytherapy. This work aims to study and develop a seed of iridium-192 from a platinum-iridium alloy The prototype seed has a 3.0 mm long core sealed by a titanium capsule of 0.8 mm of outer diameter, 0.05 mm of wall thickness and 4.5 mm long. We developed a methodology that covered: characterisation of the material used in the core, creation of a device for neutron activation of the cores and leakage tests. The results show that this methodology is feasible. As a suggestion for future work, studies regarding metrology and dosimetry of these sources should be carried out. (authors)

  8. Synthesis and electrophosphorescence of iridium complexes containing benzothiazole-based ligands.

    Science.gov (United States)

    Liu, Di; Ren, Huicai; Deng, Lijun; Zhang, Ting

    2013-06-12

    Four heteroleptic bis-cyclometalated iridium(III) complexes containing 2-aryl-benzothiazole ligands, in which the aryl is dibenzofuran-2-yl [Ir(O-bt)2(acac)], dibenzothiophene-2-yl [Ir(S-bt)2(acac)], dibenzothiophene-S,S-dioxide-2-yl [Ir(SO2-bt)2(acac)] and 4-(diphenylphosphoryl)phenyl [Ir(PO-bt)2(acac)], have been synthesized and characterized for use in organic light-emitting diodes (OLEDs). These complexes emit bright yellow (551 nm) to orange-red (598 nm) phosphorescence at room temperature, the peak wavelengths of which can be finely tuned depending upon the electronic properties of the aryl group in the 2-position of benzothiazole. The strong electron-withdrawing aryls such as dibenzothiophene-S,S-dioxide2-yl and 4-(diphenylphosphoryl)phenyl caused bathochromatic shift of the iridium complex phosphorescence. These iridium complexes were used as doped emitters to fabricate yellow to orange-red OLEDs and good performance was obtained. In particular, a maximum luminance efficiency of 58.4 cd A(-1) (corresponding to 30.6 lm W(-1) and 19%) with CIE coordinates of (0.45, 0.52) was achieved for Ir(O-bt)2(acac)-based yellow device. Furthermore, the yellow emitting Ir(S-bt)2(acac) was used to fabricate two-element white OLED that exhibited a high efficiency of 32.4 cd A(-1) with CIE coordinates of (0.28, 0.44).

  9. Synthesis and Electroluminescent Property of New Orange Iridium Compounds for Flexible White Organic Light Emitting Diodes.

    Science.gov (United States)

    Lee, Ho Won; Jeong, Hyunjin; Kim, Young Kwan; Ha, Yunkyoung

    2015-10-01

    Recently, white organic light-emitting diodes (OLEDs) have aroused considerable attention because they have the potential of next-generation flexible displays and white illuminated applications. White OLED applications are particularly heading to the industry but they have still many problems both materials and manufacturing. Therefore, we proposed that the new iridium compounds of orange emitters could be demonstrated and also applied to flexible white OLEDs for verification of potential. First, we demonstrated the chemical properties of new orange iridium compounds. Secondly, conventional two kinds of white phosphorescent OLEDs were fabricated by following devices; indium-tin oxide coated glass substrate/4,4'-bis[N-(napthyl)-N-phenylamino]biphenyl/N,N'-dicarbazolyl-3,5-benzene doped with blue and new iridium compounds for orange emitting 8 wt%/1,3,5-tris[N-phenylbenzimidazole-2-yl]benzene/lithium quinolate/aluminum. In addition, we fabricated white OLEDs using these emitters to verify the potential on flexible substrate. Therefore, this work could be proposed that white light applications can be applied and could be extended to additional research on flexible applications.

  10. Enantioselective Analysis in instruments onboard ROSETTA/PHILAE and ExoMars

    Science.gov (United States)

    Hendrik Bredehöft, Jan; Thiemann, Wolfram; Meierhenrich, Uwe; Goesmann, Fred

    It has been suggested a number of times in the past, to look for chirality as a biomarker. So far, for lack of appropriate instrumentation, space missions have never included enantioselective analysis. The distinction between enantiomers is of crucial importance to the question of the origin of the very first (pre)biotic molecules. If molecules detected in situ on another celestial body were found to exhibit a chiral bias, this would mean that at least partial asymmetric synthesis could take place abiotically. If this chiral bias should be found to be near 100For the currently flying ESA mission ROSETTA an enantioselective instrument was built, to try for the first time to detect and separate chiral molecules in situ. This instrument is COSAC, the Cometary Sampling and Acquisition Experiment, an enantioselective GCMS device[1,2], which is included in the lander PHLIAE that will eventually in 2014 land on the nucleus of comet 67P/Churyumov-Gerasimenko. A similar but even more powerful type of enantioselective GC-MS is in preparation for ESA's ExoMars mission. This instrument is part of MOMA, the Mars Organic Molecules Analyser. It has the objective of identifying and quantifying chiral organic molecules in surface and subsurface samples of Mars. Currently ExoMars is scheduled for 2018. The newly developed enantioselective technique utilized by both COSAC and MOMA will be described, including sample acquisition, derivatization, and separation in space-resistant chiral stationary capillary columns with time-of-flight mass spectrometric detection. Results of enantioselective analyses of representative test samples with special emphasis on amino acids[3], the building blocks of protein polymers, will be presented and we will discuss potential results of space missions Rosetta and ExoMars. [1] Thiemann W.H.-P., Meierhenrich U.: ESA Mission ROSETTA Will Probe for Chirality of Cometary Amino Acids. Origins of Life and Evolution of Biospheres 31 (2001), 199-210. [2

  11. Development of Iridium Solid-state Reference Electrode for the Water Chemistry Status Measurement in Nuclear Power Plants

    International Nuclear Information System (INIS)

    Ku, Heekwon; Lim, Dongseok; Cho, Jaeseon

    2013-01-01

    The result of ECP measurement of piping material in nuclear power plant at low temperature using the developed iridium (SSRE) reference electrode is approximately -0.370V. Based on the various results of this study, the developed iridium (SSRE) reference electrode can be applied to the water chemistry environments of nuclear power plant. Various metallic materials used in a nuclear power plant have been exposed to a variety of water chemistry environments and the corrosion of metallic materials occurs due to the reactions between metal structures and water chemistry environments. Therefore, the management of the water chemistry factors is needed to prevent corrosion. The chemical factors affecting the corrosion are pH and Electrochemical Corrosion Potential (ECP). The world-wide studies suggest that ECP and pH are effective indicators for preventing the material damage from water chemistry condition. ECP and pH should be measured as the reference electrodes, and should show stable potential characteristics with fast responses. In this study, the iridium reference electrodes using a solid-state metal oxide electrode has been developed to measure effective indicators such as ECP and pH. The iridium (SSRE) reference electrode for the ECP measurement in water chemistry environment of nuclear power plants has been developed. A calibration for water chemistry measurement was performed by potential measurement of iridium (SSRE) reference electrode with Ag/AgCl (SSRE) reference electrode. The result exhibited a stable potential for 117 hours and a super-Nernst ian response with 63.12mV/p H. In this study, the iridium (SSRE) reference electrode shows super-Nernst ian characteristic and it may be caused by the property of electrolytically coated iridium oxide. Considering the long-term stability of the developed electrode, it is possible to apply as a reference electrode through calibration procedure

  12. Enantioselective Diels-Alder Reaction Using Chiral Mg Complexes Derived from Chiral 2-[2-[(Alkyl- or 2-[2-[(Arylsulfonyl)amino]phenyl]-4-phenyl-1,3-oxazoline.

    Science.gov (United States)

    Ichiyanagi, Tsuyoshi; Shimizu, Makoto; Fujisawa, Tamotsu

    1997-11-14

    Magnesium complexes derived from (R)-2-[2-[(alkyl- or (R)-2-[2-[(arylsulfonyl)amino]phenyl]-4-phenyl-1,3-oxazolines and methylmagnesium iodide were found to be efficient Lewis acid catalysts for the Diels-Alder reaction of 3-alkenoyl-1,3-oxazolidin-2-one with cyclopentadiene. Chiral ligands were easily prepared from readily available D-phenylglycinol in good yields. The reaction of 3-acryloyl-1,3-oxazolidin-2-one with cyclopentadiene catalyzed by a stoichiometric amount of the Lewis acid gave exclusively the endo-cycloaddition product in up to 92% ee. The sulfonamide group on the chiral ligand strongly influenced the enantiofacial selectivity: the use of a toluene-, benzene-, 1- or 2-naphthalene-, or methanesulfonamide group in the chiral ligand gave the endo-(2R)-cycloaddition product, while a trifluoromethanesulfonamide group predominantly gave its enantiomer, the endo-(2S)-cycloaddition product, in 65% ee. The scope and limitations of the catalytic effect of chiral Mg(II) complexes on the enantioselectivity of the Diels-Alder reaction were investigated. The reaction mechanism of the Mg(II)-catalyzed reaction is also discussed on the basis of the experimental results.

  13. Evaluation of reversible interconversion in comprehensive two-dimensional gas chromatography using enantioselective columns in first and second dimensions.

    Science.gov (United States)

    Kröger, Sabrina; Wong, Yong Foo; Chin, Sung-Tong; Grant, Jacob; Lupton, David; Marriott, Philip J

    2015-07-24

    The reversible molecular interconversion behaviour of a synthesised oxime (2-phenylpropanaldehyde oxime; (C6H5)CH(CH3)CHN(OH)) was investigated by both, single dimensional gas chromatography (1D GC) and comprehensive two-dimensional gas chromatography (GC×GC). Previous studies on small molecular weight oximes were extended to this larger aromatic oxime (molar mass 149.19gmol(-1)) with interest in the extent of interconversion, enantioselective resolution, and retention time. On a polyethylene glycol (PEG; wax-type) column, a characteristic interconversion zone between two antipodes of E and Z isomers was formed by molecules which have undergone isomerisation on the column (E⇌Z). The extent of interconversion was investigated by varying chromatographic conditions (oven temperature and carrier flow rate) to understand the nature of the behaviour observed. The extent of interconversion was negligible in both enantioselective and methyl-phenylpolysiloxane phase-columns, correlating with the low polarity of the stationary phase. In order to obtain isomerisation along with enantio-resolution, a wax-type and an enantioselective column were coupled in either enantioselective-wax or wax-enantioselective order. The most appropriate column arrangement was selected for study by using a GC×GC experiment with either a wax-phase or phenyl-methylpolysiloxane phase as (2)D column. In addition to evaluation of these fast elution columns, a long narrow-bore enantioselective column (10m) was introduced as (2)D, providing an enantioselective-PEG (coupled-column ensemble: (1)D1+(1)D2)×enantioselective ((2)D) column combination. In this instance, the (1)D1 enantioselective column provides enantiomeric separation of the corresponding enantiomers ((R) and (S)) of (E)- and (Z)-2-phenylpropanaldehyde oxime, followed by E/Z isomerisation in the coupled (1)D2 PEG (reactor) column. The resulting chromatographic interconversion region was modulated and separated into either E/Z isomers

  14. NHC-Copper(I) Halide-Catalyzed Direct Alkynylation of Trifluoromethyl Ketones on Water

    KAUST Repository

    Czerwiński, Paweł

    2016-05-04

    An efficient and easily scalable NHC-copper(I) halide-catalyzed addition of terminal alkynes to 1,1,1-trifluoromethyl ketones, carried out on water for the first time, is reported. A series of addition reactions were performed with as little as 0.1-2.0mol% of [(NHC)CuX] (X=Cl, Br, I, OAc, OTf) complexes, providing tertiary propargylic trifluoromethyl alcohols in high yields and with excellent chemoselectivity from a broad range of aryl- and more challenging alkyl-substituted trifluoromethyl ketones (TFMKs). DFT calculations were performed to rationalize the correlation between the yield of catalytic alkynylation and the sterics of N-heterocyclic carbenes (NHCs), expressed as buried volume (%VBur), indicating that steric effects dominate the yield of the reaction. Additional DFT calculations shed some light on the differential reactivity of [(NHC)CuX] complexes in the alkynylation of TFMKs. The first enantioselective version of a direct alkynylation in the presence of C1-symmetric NHC-copper(I) complexes is also presented. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Strengths, Weaknesses, Opportunities and Threats: Computational Studies of Mn- and Fe-Catalyzed Epoxidations

    Directory of Open Access Journals (Sweden)

    Filipe Teixeira

    2016-12-01

    Full Text Available The importance of epoxides as synthetic intermediates in a number of highly added-value chemicals, as well as the search for novel and more sustainable chemical processes have brought considerable attention to the catalytic activity of manganese and iron complexes towards the epoxidation of alkenes using non-toxic terminal oxidants. Particular attention has been given to Mn(salen and Fe(porphyrin catalysts. While the former attain remarkable enantioselectivity towards the epoxidation of cis-alkenes, the latter also serve as an important model for the behavior of cytochrome P450, thus allowing the exploration of complex biological processes. In this review, a systematic survey of the bibliographical data for the theoretical studies on Mn- and Fe-catalyzed epoxidations is presented. The most interesting patterns and trends are reported and finally analyzed using an evaluation framework similar to the SWOT (Strengths, Weaknesses, Opportunities and Threats analysis performed in enterprise media, with the ultimate aim to provide an overview of current trends and areas for future exploration.

  16. Enantioselective desymmetrization of prochiral cyclohexanones by organocatalytic intramolecular Michael additions to α,β-unsaturated esters.

    Science.gov (United States)

    Gammack Yamagata, Adam D; Datta, Swarup; Jackson, Kelvin E; Stegbauer, Linus; Paton, Robert S; Dixon, Darren J

    2015-04-13

    A new catalytic asymmetric desymmetrization reaction for the synthesis of enantioenriched derivatives of 2-azabicyclo[3.3.1]nonane, a key motif common to many alkaloids, has been developed. Employing a cyclohexanediamine-derived primary amine organocatalyst, a range of prochiral cyclohexanone derivatives possessing an α,β-unsaturated ester moiety linked to the 4-position afforded the bicyclic products, which possess three stereogenic centers, as single diastereoisomers in high enantioselectivity (83-99% ee) and in good yields (60-90%). Calculations revealed that stepwise C-C bond formation and proton transfer via a chair-shaped transition state dictate the exclusive endo selectivity and enabled the development of a highly enantioselective primary amine catalyst. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Enantioselective apoptosis induced by individual isomers of bifenthrin in Hep G2 cells.

    Science.gov (United States)

    Liu, Huigang; Li, Juan

    2015-03-01

    Bifenthrin (BF) has been used in racemate for agricultural purposes against soil insects, leading to increased inputs into soil environments. However, most of the studies about the toxicology research on BF were performed in its racemic form. The aim of the present study was to evaluate the enantiomer-specific cis-BF-induced apoptosis and intracellular reactive oxygen species (ROS) generation on human hepatocarcinoma cells (Hep G2). The results of cell viability assay and cytoflow assay indicated an obvious enantioselective hepatocyte toxicity of 1S-cis-BF in Hep G2 cells. 1S-cis-BF also induced ROS production, up-regulated Bax protein expression and down-regulated Bcl-2 expression levels. The present study suggested that enantioselective toxicity should be evaluated on currently used chiral pesticides, such as synthetic pyrethroids. Copyright © 2015 Elsevier B.V. All rights reserved.

  18. Enantioselective Decarboxylative Alkylation Reactions: Catalyst Development, Substrate Scope, and Mechanistic Studies

    KAUST Repository

    Behenna, Douglas C.; Mohr, Justin T.; Sherden, Nathaniel H.; Marinescu, Smaranda C.; Harned, Andrew M.; Tani, Kousuke; Seto, Masaki; Ma, Sandy; Nová k, Zoltá n; Krout, Michael R.; McFadden, Ryan M.; Roizen, Jennifer L.; Enquist, John A.; White, David E.; Levine, Samantha R.; Petrova, Krastina V.; Iwashita, Akihiko; Virgil, Scott C.; Stoltz, Brian M.

    2011-01-01

    α-Quaternary ketones are accessed through novel enantioselective alkylations of allyl and propargyl electrophiles by unstabilized prochiral enolate nucleophiles in the presence of palladium complexes with various phosphinooxazoline (PHOX) ligands. Excellent yields and high enantiomeric excesses are obtained from three classes of enolate precursor: enol carbonates, enol silanes, and racemic β-ketoesters. Each of these substrate classes functions with nearly identical efficiency in terms of yield and enantioselectivity. Catalyst discovery and development, the optimization of reaction conditions, the exploration of reaction scope, and applications in target-directed synthesis are reported. Experimental observations suggest that these alkylation reactions occur through an unusual inner-sphere mechanism involving binding of the prochiral enolate nucleophile directly to the palladium center.

  19. Enantioselective construction of quaternary N-heterocycles by palladium-catalysed decarboxylative allylic alkylation of lactams

    KAUST Repository

    Behenna, Douglas C.

    2011-12-18

    The enantioselective synthesis of nitrogen-containing heterocycles (N-heterocycles) represents a substantial chemical research effort and resonates across numerous disciplines, including the total synthesis of natural products and medicinal chemistry. In this Article, we describe the highly enantioselective palladium-catalysed decarboxylative allylic alkylation of readily available lactams to form 3,3-disubstituted pyrrolidinones, piperidinones, caprolactams and structurally related lactams. Given the prevalence of quaternary N-heterocycles in biologically active alkaloids and pharmaceutical agents, we envisage that our method will provide a synthetic entry into the de novo asymmetric synthesis of such structures. As an entry for these investigations we demonstrate how the described catalysis affords enantiopure quaternary lactams that intercept synthetic intermediates previously used in the synthesis of the Aspidosperma alkaloids quebrachamine and rhazinilam, but that were previously only available by chiral auxiliary approaches or as racemic mixtures. © 2012 Macmillan Publishers Limited. All rights reserved.

  20. Enantioselective Decarboxylative Alkylation Reactions: Catalyst Development, Substrate Scope, and Mechanistic Studies

    Science.gov (United States)

    Behenna, Douglas C.; Mohr, Justin T.; Sherden, Nathaniel H.; Marinescu, Smaranda C.; Harned, Andrew M.; Tani, Kousuke; Seto, Masaki; Ma, Sandy; Novák, Zoltán; Krout, Michael R.; McFadden, Ryan M.; Roizen, Jennifer L.; Enquist, John A.; White, David E.; Levine, Samantha R.; Petrova, Krastina V.; Iwashita, Akihiko; Virgil, Scott C.; Stoltz, Brian M.

    2012-01-01

    α-Quaternary ketones are accessed through novel enantioselective alkylations of allyl and propargyl electrophiles by unstabilized prochiral enolate nucleophiles in the presence of palladium complexes with various phosphinooxazoline (PHOX) ligands. Excellent yields and high enantiomeric excesses are obtained from three classes of enolate precursors: enol carbonates, enol silanes, and racemic β-ketoesters. Each of these substrate classes functions with nearly identical efficiency in terms of yield and enantioselectivity. Catalyst discovery and development, the optimization of reaction conditions, the exploration of reaction scope, and applications in target-directed synthesis are reported. Experimental observations suggest that these alkylation reactions occur through an unusual inner-sphere mechanism involving binding of the prochiral enolate nucleophile directly to the palladium center. PMID:22083969

  1. Enantioselective Decarboxylative Alkylation Reactions: Catalyst Development, Substrate Scope, and Mechanistic Studies

    KAUST Repository

    Behenna, Douglas C.

    2011-11-14

    α-Quaternary ketones are accessed through novel enantioselective alkylations of allyl and propargyl electrophiles by unstabilized prochiral enolate nucleophiles in the presence of palladium complexes with various phosphinooxazoline (PHOX) ligands. Excellent yields and high enantiomeric excesses are obtained from three classes of enolate precursor: enol carbonates, enol silanes, and racemic β-ketoesters. Each of these substrate classes functions with nearly identical efficiency in terms of yield and enantioselectivity. Catalyst discovery and development, the optimization of reaction conditions, the exploration of reaction scope, and applications in target-directed synthesis are reported. Experimental observations suggest that these alkylation reactions occur through an unusual inner-sphere mechanism involving binding of the prochiral enolate nucleophile directly to the palladium center.

  2. Enantioselective cytotoxicity of the insecticide bifenthrin on a human amnion epithelial (FL) cell line

    International Nuclear Information System (INIS)

    Liu Huigang; Zhao Meirong; Zhang Cong; Ma Yun; Liu Weiping

    2008-01-01

    Synthetic pyrethroids (SPs) are used in preference to organochlorines and organophosphates due to their high efficiency, low toxicity to mammals, and ready biodegradability. Previous studies reported that enantioselective toxicity of SPs occurs in aquatic toxicity. Several studies have indicated that SPs could lead to oxidative damage in humans or animals which was associated with their toxic effects. Little is known about the differences in the effects of chronic toxicity induced by individual stereoisomers of chiral SPs. The present study was therefore undertaken to evaluate the enantioselectivity in cytotoxicity, genotoxicity caused by bifenthrin (BF) on human amnion epithelial (FL) cell lines and pesticidal activity on target organism. The cell proliferation and cytoflow analysis indicated that 1S-cis-BF presented more toxic effects than 1R-cis-BF above the concentration of 7.5 mg L -1 (p > 0.05). FL cells incubated with 1S-cis-BF exhibited a dose-dependent accumulation of intracellular reactive oxygen species (ROS). In the comet assay, the number of cells with damaged DNA incubated with 1S-cis-BF was more than that with 1R-cis-BF (p 50 values of enantiomer to the target pest on Pieris rapae L. show that 1R-cis-BF was 300 times more active than 1S-cis-BF. These results indicate that the enantioselective toxicity and activity of BF between non-target organism and target organism was reversal. These implications together suggest that assessment of the environmental safety and new pesticides development with chiral centers should consider enantioselectivity

  3. Synthesis of 3-fluoro-3-aryl oxindoles: Direct enantioselective α arylation of amides

    KAUST Repository

    Wu, Linglin; Falivene, Laura; Drinkel, Emma E.; Grant, Sharday; Linden, Anthony; Cavallo, Luigi; Dorta, Reto

    2012-01-01

    Modus operandi: Catalytic access to the title compounds through a new asymmetric α-arylation protocol is reported (see scheme). These products are formed in good yields and excellent enantioselectivities by using a new and easily synthesized chiral N-heterocyclic carbene (NHC) ligand. Advanced DFT calculations reveal the properties of the NHC ligand and the mode of operation of the catalyst. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Effects of metals on enantioselective toxicity and biotransformation of cis-bifenthrin in zebrafish.

    Science.gov (United States)

    Yang, Ye; Ji, Dapeng; Huang, Xin; Zhang, Jianyun; Liu, Jing

    2017-08-01

    Co-occurrence of pyrethroids and metals in watersheds previously has been reported to pose great risk to aquatic species. Pyrethroids are a class of chiral insecticides that have been shown to have enantioselective toxicity and biotransformation. However, the influence of metals on enantioselectivity of pyrethroids has not yet been evaluated. In the present study, the effects of cadmium (Cd), copper (Cu), and lead (Pb) on the enantioselective toxicity and metabolism of cis-bifenthrin (cis-BF) were investigated in zebrafish at environmentally relevant concentrations. The addition of Cd, Cu, or Pb significantly increased the mortality of zebrafish in racemate and R-enantiomer of cis-BF-treated groups. In rac-cis-BF- or 1R-cis-BF-treated groups, the addition of Cd, Cu, or Pb caused a decrease in enantiomeric fraction (EF) and an increased ratio of R-enantiomer residues in zebrafish. In 1S-cis-BF-treated groups, coexposure to Cd led to a lower EF and decreased residue levels of S-enantiomer. In addition, coexposure to the 3 metals resulted in different biodegradation characteristics of each enantiomer accompanied with differential changes in the expression of cytochrome P450 (CYP)1, CYP2, and CYP3 genes, which might be responsible for the enantioselective biodegradation of cis-BF in zebrafish. These results suggest that the influence of coexistent metals should be considered in the ecological risk assessment of chiral pyrethroids in aquatic environments. Environ Toxicol Chem 2017;36:2139-2146. © 2017 SETAC. © 2017 SETAC.

  5. A combined continuous microflow photochemistry and asymmetric organocatalysis approach for the enantioselective synthesis of tetrahydroquinolines

    Directory of Open Access Journals (Sweden)

    Erli Sugiono

    2013-11-01

    Full Text Available A continuous-flow asymmetric organocatalytic photocyclization–transfer hydrogenation cascade reaction has been developed. The new protocol allows the synthesis of tetrahydroquinolines from readily available 2-aminochalcones using a combination of photochemistry and asymmetric Brønsted acid catalysis. The photocylization and subsequent reduction was performed with catalytic amount of chiral BINOL derived phosphoric acid diester and Hantzsch dihydropyridine as hydrogen source providing the desired products in good yields and with excellent enantioselectivities.

  6. Enantioselective analysis of drugs: contributions of high-performance liquid chromatography and capillary electrophoresis

    OpenAIRE

    Bonato, Pierina Sueli; Jabor, Valquíria Aparecida Polisel; Gaitani, Cristiane Masetto de

    2005-01-01

    The demand for analytical methods suitable for accurate and reproducible determination of drug enantiomers has increased significantly in the last years. High-performance liquid chromatography (HPLC) using chiral stationary phases and capillary electrophoresis (CE) are the most important techniques used for this purpose. In this paper, the fundamental aspects of chiral separations using both techniques are presented. Some important aspects for the development of enantioselective methods, part...

  7. Enantioselective synthesis of the novel chiral sulfoxide derivative as a glycogen synthase kinase 3beta inhibitor.

    Science.gov (United States)

    Saitoh, Morihisa; Kunitomo, Jun; Kimura, Eiji; Yamano, Toru; Itoh, Fumio; Kori, Masakuni

    2010-09-01

    Glycogen synthase kinase 3beta (GSK-3beta) inhibitors are expected to be attractive therapeutic agents for the treatment of Alzheimer's disease (AD). Recently we discovered sulfoxides (S)-1 as a novel GSK-3beta inhibitor having in vivo efficacy. We investigated practical asymmetric preparation methods for the scale-up synthesis of (S)-1. The highly enantioselective synthesis of (S)-1 (94% ee) was achieved by titanium-mediated oxidation with D-(-)-diethyl tartrate on gram scale.

  8. Synthesis of 3-fluoro-3-aryl oxindoles: Direct enantioselective α arylation of amides

    KAUST Repository

    Wu, Linglin

    2012-02-06

    Modus operandi: Catalytic access to the title compounds through a new asymmetric α-arylation protocol is reported (see scheme). These products are formed in good yields and excellent enantioselectivities by using a new and easily synthesized chiral N-heterocyclic carbene (NHC) ligand. Advanced DFT calculations reveal the properties of the NHC ligand and the mode of operation of the catalyst. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Can laccases catalyze bond cleavage in lignin?

    DEFF Research Database (Denmark)

    Munk, Line; Sitarz, Anna Katarzyna; Kalyani, Dayanand

    2015-01-01

    illustrations of the putative laccase catalyzed reactions, including the possible reactions of the reactive radical intermediates taking place after the initial oxidation of the phenol-hydroxyl groups, we show that i) Laccase activity is able to catalyze bond cleavage in low molecular weight phenolic lignin......-substituted phenols, benzenethiols, polyphenols, and polyamines, which may be oxidized. In addition, the currently available analytical methods that can be used to detect enzyme catalyzed changes in lignin are summarized, and an improved nomenclature for unequivocal interpretation of the action of laccases on lignin...

  10. Phytotoxicity of chiral herbicide bromacil: Enantioselectivity of photosynthesis in Arabidopsis thaliana

    International Nuclear Information System (INIS)

    Chen, Zunwei; Zou, Yuqin; Wang, Jia; Li, Meichao; Wen, Yuezhong

    2016-01-01

    With the wide application of chiral herbicides and the frequent detection of photosystem II (PSII) herbicides, it is of great importance to assess the direct effects of PSII herbicides on photosynthesis in an enantiomeric level. In the present study, the enantioselective phytotoxicity of bromacil (BRO), typical photosynthesis inhibition herbicide, on Arabidopsis thaliana was investigated. The results showed that S-BRO exhibited a greater inhibition of electron transmission in photosystem I (PSI) of A. thaliana than R-BRO by inhibiting the transcription of fnr 1. S-BRO also changed the chlorophyll fluorescence parameters Y (II), Y (NO), and Y (NPQ) to a greater extent than R-Bro. Transcription of genes psbO2, Lhcb3 and Lhcb6 was down-regulated in an enantioselective rhythm and S-BRO caused more serious influence, indicating that S-BRO did worse damage to the photosystem II (PSII) of A. thaliana than R-BRO. This study suggested that S-BRO disturbed the photosynthesis of plants to a larger extent than R-BRO and provided a new sight to evaluate the phytotoxicity of chiral herbicides. - Highlights: • It is necessary to assess the direct effects of PSII herbicides on photosynthesis. • Phytotoxicity of bromacil is investigated in an enantiomeric level. • Bromacil disturbed enantioselectively the photosystem II of Arabidopsis thaliana. • S-bromacil caused severer damage to photosynthesis of Arabidopsis than R-bromacil. • Photosynthesis should be considered for phytotoxicity assessment of herbicides.

  11. Phytotoxicity of chiral herbicide bromacil: Enantioselectivity of photosynthesis in Arabidopsis thaliana

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Zunwei; Zou, Yuqin; Wang, Jia [MOE Key Laboratory of Environmental Remediation & Ecosystem Health, College of Environmental and Resource Sciences, Zhejiang University, Hangzhou 310058 (China); Li, Meichao [Research Center of Analysis and Measurement, Zhejiang University of Technology, Hangzhou 310032 (China); Wen, Yuezhong, E-mail: wenyuezhong@zju.edu.cn [MOE Key Laboratory of Environmental Remediation & Ecosystem Health, College of Environmental and Resource Sciences, Zhejiang University, Hangzhou 310058 (China)

    2016-04-01

    With the wide application of chiral herbicides and the frequent detection of photosystem II (PSII) herbicides, it is of great importance to assess the direct effects of PSII herbicides on photosynthesis in an enantiomeric level. In the present study, the enantioselective phytotoxicity of bromacil (BRO), typical photosynthesis inhibition herbicide, on Arabidopsis thaliana was investigated. The results showed that S-BRO exhibited a greater inhibition of electron transmission in photosystem I (PSI) of A. thaliana than R-BRO by inhibiting the transcription of fnr 1. S-BRO also changed the chlorophyll fluorescence parameters Y (II), Y (NO), and Y (NPQ) to a greater extent than R-Bro. Transcription of genes psbO2, Lhcb3 and Lhcb6 was down-regulated in an enantioselective rhythm and S-BRO caused more serious influence, indicating that S-BRO did worse damage to the photosystem II (PSII) of A. thaliana than R-BRO. This study suggested that S-BRO disturbed the photosynthesis of plants to a larger extent than R-BRO and provided a new sight to evaluate the phytotoxicity of chiral herbicides. - Highlights: • It is necessary to assess the direct effects of PSII herbicides on photosynthesis. • Phytotoxicity of bromacil is investigated in an enantiomeric level. • Bromacil disturbed enantioselectively the photosystem II of Arabidopsis thaliana. • S-bromacil caused severer damage to photosynthesis of Arabidopsis than R-bromacil. • Photosynthesis should be considered for phytotoxicity assessment of herbicides.

  12. Computer-Assisted Design and Synthetic Applications of Chiral Enol Borinates: Novel, Highly Enantioselective Aldol Reagents

    Directory of Open Access Journals (Sweden)

    Gennari Cesare

    1998-01-01

    Full Text Available We have recently described the development of a quantitative transition state model for the prediction of stereoselectivity in the boron-mediated aldol reaction. This model provides qualitative insights into the factors contributing to the stereochemical outcome of a variety of reactions of synthetic importance. The force field model was used to assist the design and preparation of new chiral boron ligands derived from menthone. The chiral boron enolates were employed in various stereoselective processes, including the addition to chiral aldehydes and the reagent-controlled total synthesis of (3S,4S-statine. The chiral enolates derived from alpha-halo and alpha-oxysubstituted thioacetates were added to aldehydes and imines. Addition to imines leads to the enantioselective synthesis of chiral aziridines, a formal total synthesis of (+-thiamphenicol, and a new highly efficient synthesis of the paclitaxel (taxol® C-13 side-chain and taxol semisynthesis from baccatin III. The stereochemical outcome of the addition to imines was rationalised with the aid of computational studies. Enantioselective addition reactions of the chiral boron enolate derived from thioacetate have successfully been applied to solid phase bound aldehydes to give aldol products in comparable yields and enantioselectivities to the usual solution conditions.

  13. Modelling substrate specificity and enantioselectivity for lipases and esterases by substrate-imprinted docking

    Directory of Open Access Journals (Sweden)

    Tyagi Sadhna

    2009-06-01

    Full Text Available Abstract Background Previously, ways to adapt docking programs that were developed for modelling inhibitor-receptor interaction have been explored. Two main issues were discussed. First, when trying to model catalysis a reaction intermediate of the substrate is expected to provide more valid information than the ground state of the substrate. Second, the incorporation of protein flexibility is essential for reliable predictions. Results Here we present a predictive and robust method to model substrate specificity and enantioselectivity of lipases and esterases that uses reaction intermediates and incorporates protein flexibility. Substrate-imprinted docking starts with covalent docking of reaction intermediates, followed by geometry optimisation of the resulting enzyme-substrate complex. After a second round of docking the same substrate into the geometry-optimised structures, productive poses are identified by geometric filter criteria and ranked by their docking scores. Substrate-imprinted docking was applied in order to model (i enantioselectivity of Candida antarctica lipase B and a W104A mutant, (ii enantioselectivity and substrate specificity of Candida rugosa lipase and Burkholderia cepacia lipase, and (iii substrate specificity of an acetyl- and a butyrylcholine esterase toward the substrates acetyl- and butyrylcholine. Conclusion The experimentally observed differences in selectivity and specificity of the enzymes were reproduced with an accuracy of 81%. The method was robust toward small differences in initial structures (different crystallisation conditions or a co-crystallised ligand, although large displacements of catalytic residues often resulted in substrate poses that did not pass the geometric filter criteria.

  14. Enantioselective Characteristics and Montmorillonite-Mediated Removal Effects of α-Hexachlorocyclohexane in Laying Hens.

    Science.gov (United States)

    Liu, Xueke; Shen, Zhigang; Wang, Peng; Liu, Chang; Yao, Guojun; Zhou, Zhiqiang; Liu, Donghui

    2016-06-07

    α-Hexachlorocyclohexane (α-HCH) is a chiral organochlorine pesticide that is often ubiquitously detected in various environmental matrices and may be absorbed by the human body via food consumption, with serious detriments to human health. In this study, enantioselective degradation kinetics and residues of α-HCH in laying hens were investigated after a single dose of exposure to the pesticide, whereas enantioselectivity and residues of α-HCH in eggs, droppings, and various tissues were investigated after long-term exposure. Meanwhile, montmorillonite (MMT), a feed additive with high capacity of adsorption, was investigated for its ability to remove α-HCH from laying hens. Most non-brain tissues enantioselectively accumulated (-)-α-HCH, while (+)-α-HCH was preferentially accumulated in the brain. The enantiomer fractions (EFs) in most tissues gradually decreased, implying continuous depletion of (+)-α-HCH in laying hens. After 30 days of exposure and 31 days of elimination, the concentration of α-HCH in eggs and tissues of laying hens with MMT-containing feed was lower than that with MMT-free feed, indicating the removal effects of MMT for α-HCH in laying hens. The findings presented herein suggest that modified MMT may potentially be useful in reducing the enrichment of α-HCH in laying hens and eggs, thus lowering the risk of human intake of α-HCH.

  15. Asymmetric Diels-Alder Reaction of α,β-Unsaturated Oxazolidin-2-one Derivatives Catalyzed by a Chiral Fe(III)-Bipyridine Diol Complex.

    Science.gov (United States)

    Li, Mao; Carreras, Virginie; Jalba, Angela; Ollevier, Thierry

    2018-02-16

    An asymmetric Fe III -bipyridine diol catalyzed Diels-Alder reaction of α,β-unsaturated oxazolidin-2-ones has been developed. Among various Fe II /Fe III salts, Fe(ClO 4 ) 3 ·6H 2 O was selected as the Lewis acid of choice. The use of a low catalyst loading (2 mol % of Fe(ClO 4 ) 3 ·6H 2 O and 2.4 mol % of Bolm's ligand) afforded high yields (up to 99%) and high enantiomeric excesses (up to 98%) of endo-cycloadducts for the Diels-Alder reaction between cyclopentadiene and substituted acryloyloxazolidin-2-ones. Other noncyclic dienes led to decreased enantioselectivities. A proposed model supports the observed stereoinduction.

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

    Science.gov (United States)

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

    2017-04-11

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

  17. Aerobic Asymmetric Dehydrogenative Cross-Coupling between Two C(sp3)-H Groups Catalyzed by a Chiral-at-Metal Rhodium Complex.

    Science.gov (United States)

    Tan, Yuqi; Yuan, Wei; Gong, Lei; Meggers, Eric

    2015-10-26

    A sustainable C-C bond formation is merged with the catalytic asymmetric generation of one or two stereocenters. The introduced catalytic asymmetric cross-coupling of two C(sp3)-H groups with molecular oxygen as the oxidant profits from the oxidative robustness of a chiral-at-metal rhodium(III) catalyst and exploits an autoxidation mechanism or visible-light photosensitized oxidation. In the latter case, the catalyst serves a dual function, namely as a chiral Lewis acid for catalyzing enantioselective enolate chemistry and at the same time as a visible-light-driven photoredox catalyst. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Study of neutron deficient iridium isotopes by using laser spectroscopy; Etude des noyaux d'iridium deficients en neutrons par spectroscopie laser

    Energy Technology Data Exchange (ETDEWEB)

    Verney, D

    2000-12-19

    Resonance ionization spectroscopy was performed on neutron deficient iridium isotopes {sup 182-189}Ir, {sup 186}Ir{sup m} and stable isotopes {sup 191,193}Ir. Hyperfine spectra were recorded from the optical transition at 351,7 nm between the 5d{sup 7}6s{sup 2} {sup 4}F{sub 9/2} ground state and the 5d{sup 7}6s6p {sup 6}F{sub 11/2} excited state. Radioactive iridium isotopes were obtained from {beta}{sup +}/EC decay of radioactive mercury nuclei deposited on a graphite substrate. The radioactive mercury nuclei were produced at the ISOLDE facility at CERN through spallation reactions, by bombarding a molten lead target with the 1 GeV proton beam delivered by the PS-Booster. Magnetic dipole moments and spectroscopic quadrupole moments were extracted from the hyperfine spectra. The mean square charge radius variations, as deduced from the measured isotopic shift, show a sharp change between {sup 187}Ir and {sup 186}Ir{sup g}, accompanied by a sudden increase in deformation: from {beta}2 {approx} 0,16 to {beta}2 > 0, 2. These results were analysed in the framework of an axial rotor plus one or two quasiparticles. The wave functions of the osmium and platinum cores which are used in order to describe the iridium nuclei were calculated from the HF+BCS method with the Skyrme SIII effective interaction. The cores were constrained to take the deformation parameters extracted from the isotopic shift measurements. One shows then that this sudden deformation change corresponds also to a change in the proton state that describes the odd nuclei ground state or that participates in the coupling with the neutron in odd-odd nuclei. This state is identified with the {pi}3/2{sup +}[402] orbital for the smaller deformations nuclei and with the {pi}1/2{sup -}[541] orbital stemming from the h{sub 9/2} subshell for bigger deformations nuclei. (author)

  19. Development of accurate mass spectrometric routine and reference methods for the determination of trace amounts of iridium and rhodium in photographic emulsionsf

    NARCIS (Netherlands)

    Krystek, Petra; Heumann, Klaus G.

    1999-01-01

    For the determination of trace amounts of iridium and rhodium in photographic emulsions different sample treatment procedures were coupled with inductively coupled plasma mass spectrometry (ICP-MS) and, for iridium, also with negative thermal ionisation isotope dilution mass spectrometry (NTI-IDMS)

  20. Cobalt-Catalyzed C(sp(2))-H Borylation: Mechanistic Insights Inspire Catalyst Design.

    Science.gov (United States)

    Obligacion, Jennifer V; Semproni, Scott P; Pappas, Iraklis; Chirik, Paul J

    2016-08-24

    A comprehensive study into the mechanism of bis(phosphino)pyridine (PNP) cobalt-catalyzed C-H borylation of 2,6-lutidine using B2Pin2 (Pin = pinacolate) has been conducted. The experimentally observed rate law, deuterium kinetic isotope effects, and identification of the catalyst resting state support turnover limiting C-H activation from a fully characterized cobalt(I) boryl intermediate. Monitoring the catalytic reaction as a function of time revealed that borylation of the 4-position of the pincer in the cobalt catalyst was faster than arene borylation. Cyclic voltammetry established the electron withdrawing influence of 4-BPin, which slows the rate of C-H oxidative addition and hence overall catalytic turnover. This mechanistic insight inspired the next generation of 4-substituted PNP cobalt catalysts with electron donating and sterically blocking methyl and pyrrolidinyl substituents that exhibited increased activity for the C-H borylation of unactivated arenes. The rationally designed catalysts promote effective turnover with stoichiometric quantities of arene substrate and B2Pin2. Kinetic studies on the improved catalyst, 4-(H)2BPin, established a change in turnover limiting step from C-H oxidative addition to C-B reductive elimination. The iridium congener of the optimized cobalt catalyst, 6-(H)2BPin, was prepared and crystallographically characterized and proved inactive for C-H borylation, a result of the high kinetic barrier for reductive elimination from octahedral Ir(III) complexes.

  1. Muon-catalyzed fusion revisited

    Energy Technology Data Exchange (ETDEWEB)

    Anon.

    1984-12-15

    A negative muon can induce nuclear fusion in the reaction of deuteron and triton nuclei giving a helium nucleus, a neutron and an emerging negative muon. The muon forms a tightlybound deuteron-triton-muon molecule and fusion follows in about 10{sup -12}s. Then the muon is free again to induce further reactions. Thus the muon can serve as a catalyst for nuclear fusion, which can proceed without the need for the high temperatures which are needed in the confinement and inertial fusion schemes. At room temperature, up to 80 fusions per muon have recently been observed at the LAMPF machine at Los Alamos, and it is clear that this number can be exceeded. These and other results were presented at a summer Workshop on Muon-Catalyzed Fusion held in Jackson, Wyoming. Approximately fifty scientists attended from Austria, Canada, India, Italy, Japan, South Africa, West Germany, and the United States. The Workshop itself is symbolic of the revival of interest in this subject.

  2. Iron Catalyzed Cycloaddition of Alkynenitriles and Alkynes

    Science.gov (United States)

    D’Souza, Brendan R.; Lane, Timothy K.

    2011-01-01

    The combination of Fe(OAc)2 and an electron-donating, sterically-hindered pyridyl bisimine ligand catalyzes the cycloaddition of alkynenitriles and alkynes. A variety of substituted pyridines were obtained in good yields. PMID:21557582

  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. Exploiting nanospace for asymmetric catalysis: confinement of immobilized, single-site chiral catalysts enhances enantioselectivity.

    Science.gov (United States)

    Thomas, John Meurig; Raja, Robert

    2008-06-01

    In the mid-1990s, it became possible to prepare high-area silicas having pore diameters controllably adjustable in the range ca. 20-200 Å. Moreover, the inner walls of these nanoporous solids could be functionalized to yield single-site, chiral, catalytically active organometallic centers, the precise structures of which could be determined using in situ X-ray absorption and FTIR and multinuclear magic angle spinning (MAS) NMR spectroscopy. This approach opened up the prospect of performing heterogeneous enantioselective conversions in a novel manner, under the spatial restrictions imposed by the nanocavities within which the reactions occur. In particular, it suggested an alternative method for preparing pharmaceutically and agrochemically useful asymmetric products by capitalizing on the notion, initially tentatively perceived, that spatial confinement of prochiral reactants (and transition states formed at the chiral active center) would provide an altogether new method of boosting the enantioselectivity of the anchored chiral catalyst. Initially, we anchored chiral single-site heterogeneous catalysts to nanopores covalently via a ligand attached to Pd(II) or Rh(I) centers. Later, we employed a more convenient and cheaper electrostatic method, relying in part on strong hydrogen bonding. This Account provides many examples of these processes, encompassing hydrogenations, oxidations, and aminations. Of particular note is the facile synthesis from methyl benzoylformate of methyl mandelate, which is a precursor in the synthesis of pemoline, a stimulant of the central nervous system; our procedure offers several viable methods for reducing ketocarboxylic acids. In addition to relying on earlier (synchrotron-based) in situ techniques for characterizing catalysts, we have constructed experimental procedures involving robotically controlled catalytic reactors that allow the kinetics of conversion and enantioselectivity to be monitored continually, and we have access to

  5. Development of U.S. Government General Technical Requirements for UAS Flight Safety Systems Utilizing the Iridium Satellite Constellation

    Science.gov (United States)

    Murray, Jennifer; Birr, Richard

    2010-01-01

    This slide presentation reviews the development of technical requirements for Unmanned Aircraft Systems (UAS) utilization of the Iridium Satellite Constellation to provide flight safety. The Federal Aviation Authority (FAA) required an over-the-horizon communication standard to guarantee flight safety before permitting widespread UAS flights in the National Air Space (NAS). This is important to ensure reliable control of UASs during loss-link and over-the-horizon scenarios. The core requirement was to utilize a satellite system to send GPS tracking data and other telemetry from a flight vehicle down to the ground. Iridium was chosen as the system because it is one of the only true satellite systems that has world wide coverage, and the service has a highly reliable link margin. The Iridium system, the flight modems, and the test flight are described.

  6. Enantioselective Effects of Metalaxyl Enantiomers on Breast Cancer Cells Metabolic Profiling Using HPLC-QTOF-Based Metabolomics

    Directory of Open Access Journals (Sweden)

    Ping Zhang

    2017-01-01

    Full Text Available In this study, an integrative high-performance liquid chromatography coupled with quadrupole time-of-flight tandem mass spectrometry (HPLC-QTOF based metabolomics approach was performed to evaluate the enantioselective metabolic perturbations in MCF-7 cells after treatment with R-metalaxyl and S-metalaxyl, respectively. Untargeted metabolomics profile, multivariate pattern recognition, metabolites identification, and pathway analysis were determined after metalaxyl enantiomer exposure. Principal component analysis (PCA and partitial least-squares discriminant analysis (PLS-DA directly reflected the enantioselective metabolic perturbations induced by metalaxyl enantiomers. On the basis of multivariate statistical results, a total of 49 metabolites including carbohydrates, amino acids, nucleotides, fatty acids, organic acids, phospholipids, indoles, derivatives, etc. were found to be the most significantly changed metabolites and metabolic fluctuations caused by the same concentration of R-metalaxyl and S-metalaxyl were enantioselective. Pathway analysis indicated that R-metalaxyl and S-metalaxyl mainly affected the 7 and 10 pathways in MCF-7 cells, respectively, implying the perturbed pathways induced by metalaxyl enantiomers were also enantioselective. Furthermore, the significantly perturbed metabolic pathways were highly related to energy metabolism, amino acid metabolism, lipid metabolism, and antioxidant defense. Such results provide more specific insights into the enantioselective metabolic effects of chiral pesticides in breast cancer progression, reveal the underlying mechanisms, and provide available data for the health risk assessments of chiral environmental pollutants at the molecular level.

  7. Nuclear resonance scattering study of iridates, iridium and antimony based pyrochlores

    International Nuclear Information System (INIS)

    Alexeev, P.

    2017-04-01

    This thesis shows the first synchrotron-based Moessbauer spectroscopy studies on iridium containing compounds and first vibrational spectroscopy on Sb containing compounds carried out at the P01 beamline of PETRA III. In this context, two types of X-ray monochromators have been developed: a monochromator for 73 keV photons with medium energy resolution, and a high-resolution backscattering monochromator based on a sapphire crystal. The monochromator for 73 keV X-rays is the key instrument for hyperfine spectroscopy on Iridium compounds, while the sapphire backscattering monochromator is purposed to vibrational spectroscopy on any Moessbauer resonances with the transition energies in the 20-50 keV range. Additionally, the signal detection for nuclear resonance scattering experiments at the beamline was significantly improved during this work, inspired by the high energies and low lifetimes of the employed resonances. The first synchrotron-based hyperfine spectroscopy on Iridium-containing compounds was demonstrated by NRS on 73 keV resonance in "1"9"3Ir. The results can be interpreted by dynamical theory of nuclear resonance scattering. In this work, special emphasis is set onto the electronic and magnetic properties of Ir nuclei in IrO_2 and in Ruddlesden-Popper (RP) phases of strontium iridates Sr_n_+_1Ir_nO_3_n_+_1 (n=0,1). These systems are well-suited for studies with X-ray scattering techniques, since the scattered signal contains vast information about the widely tunable crystallographic and electronic structure of these systems; furthermore, studies with X-rays are less limited by absorption from iridium as it is the case for neutron scattering experiments. The hyperfine parameters in IrO_2, SrIrO_3 and Sr_2IrO_4 have been measured via Nuclear Forward Scattering for the first time. Using the dynamical theory of NRS, the temperature and magnetic field dependence of the electric field gradient and magnetic hyperfine field on Ir nucleus have been determined for

  8. Nuclear resonance scattering study of iridates, iridium and antimony based pyrochlores

    Energy Technology Data Exchange (ETDEWEB)

    Alexeev, P.

    2017-04-15

    This thesis shows the first synchrotron-based Moessbauer spectroscopy studies on iridium containing compounds and first vibrational spectroscopy on Sb containing compounds carried out at the P01 beamline of PETRA III. In this context, two types of X-ray monochromators have been developed: a monochromator for 73 keV photons with medium energy resolution, and a high-resolution backscattering monochromator based on a sapphire crystal. The monochromator for 73 keV X-rays is the key instrument for hyperfine spectroscopy on Iridium compounds, while the sapphire backscattering monochromator is purposed to vibrational spectroscopy on any Moessbauer resonances with the transition energies in the 20-50 keV range. Additionally, the signal detection for nuclear resonance scattering experiments at the beamline was significantly improved during this work, inspired by the high energies and low lifetimes of the employed resonances. The first synchrotron-based hyperfine spectroscopy on Iridium-containing compounds was demonstrated by NRS on 73 keV resonance in {sup 193}Ir. The results can be interpreted by dynamical theory of nuclear resonance scattering. In this work, special emphasis is set onto the electronic and magnetic properties of Ir nuclei in IrO{sub 2} and in Ruddlesden-Popper (RP) phases of strontium iridates Sr{sub n+1}Ir{sub n}O{sub 3n+1} (n=0,1). These systems are well-suited for studies with X-ray scattering techniques, since the scattered signal contains vast information about the widely tunable crystallographic and electronic structure of these systems; furthermore, studies with X-rays are less limited by absorption from iridium as it is the case for neutron scattering experiments. The hyperfine parameters in IrO{sub 2}, SrIrO{sub 3} and Sr{sub 2}IrO{sub 4} have been measured via Nuclear Forward Scattering for the first time. Using the dynamical theory of NRS, the temperature and magnetic field dependence of the electric field gradient and magnetic hyperfine field

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

    Directory of Open Access Journals (Sweden)

    Dominik Lenhart

    2014-04-01

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

  10. Techniques for Achieving Zero Stress in Thin Films of Iridium, Chromium, and Nickel

    Science.gov (United States)

    Broadway, David M.; O'Dell, Stephen L.; Ramsey, Brian D.; Weimer, Jeffrey

    2015-01-01

    We examine techniques for achieving zero intrinsic stress in thin films of iridium, chromium, and nickel deposited by magnetron sputter deposition. The intrinsic stress is further correlated to the microstructural features and physical properties such as surface roughness and optical density at a scale appropriate to soft X-ray wavelengths. The examination of the stress in these materials is motivated by efforts to advance the optical performance of light-weight X-ray space telescopes into the regime of sub-arcsecond resolution through various deposition techniques that rely on control of the film stress to values within 10-100 MPa. A characteristic feature of the intrinsic stress behavior in chromium and nickel is their sensitivity to the magnitude and sign of the intrinsic stress with argon gas pressure and deposition rate, including the existence of a critical argon process pressure that results in zero film stress which scales linearly with the atomic mass of the sputtered species. While the effect of stress reversal with argon pressure has been previously reported by Hoffman and others for nickel and chromium, we report this effect for iridium. In addition to stress reversal, we identify zero stress in the optical functioning iridium layer shortly after island coalescence for low process pressures at a film thickness of approximately 35nm. The measurement of the low values of stress during deposition was achieved with the aid of a sensitive in-situ instrument capable of a minimum detectable level of stress, assuming a 35nm thick film, in the range of 0.40-6.0 MPa for oriented crystalline silicon substrate thicknesses of 70-280 microns, respectively.

  11. A colorimetric and luminescent dual-modal assay for Cu(II ion detection using an iridium(III complex.

    Directory of Open Access Journals (Sweden)

    Dik-Lung Ma

    Full Text Available A novel iridium(III complex-based chemosensor bearing the 5,6-bis(salicylideneimino-1,10-phenanthroline ligand receptor was developed, which exhibited a highly sensitive and selective color change from colorless to yellow and a visible turn-off luminescence response upon the addition of Cu(II ions. The interactions of this iridium(III complex with Cu2+ ions and thirteen other cations have been investigated by UV-Vis absorption titration, emission titration, and 1H NMR titration.

  12. Synthesis and structural studies of Cp{sup *} rhodium and Cp{sup *} iridium complexes of picolinic hydrazine ligand

    Energy Technology Data Exchange (ETDEWEB)

    Palepu, Narasinga Rao; Kollipara, Mohan Rao [Centre for Advanced Studies in Chemistry, North-Eastern Hill University, Shillong (India); Kaminsky Werner [Dept. of Chemistry, University of Washington, Seattle (United States)

    2017-01-15

    A series of Cp{sup *}Rh and Cp{sup *}Ir complexes of picolinic hydrazine ligand are synthesized and characterized. Picolinic hydrazine has yielded only dinuclear complexes in the case of rhodium metal whereas both mono and dinuclear complexes with iridium metal. Iridium complexes are formed as quaternary salts by the migration of the N–H proton onto the adjacent amine group of the hydrazine after binding to the metal. Picolinic hydrazine acts as nitrogen and oxygen donor ligand in the form of bi and tetradentate bonding modes.

  13. Palynological and iridium anomalies at Cretaceous-Tertiary boundary, south-central Saskatchewan

    Science.gov (United States)

    Nichols, D.J.; Jarzen, D.M.; Orth, C.J.; Oliver, P.Q.

    1986-01-01

    The Cretaceous-Tertiary boundary in south-central Saskatchewan is marked by coincident anomalies in abundance of iridium and fern spores at the extinction level of a suite of Cretaceous pollen taxa. Evidence of disruption of the terrestrial flora includes the fern-spore abundance anomaly and local extinction of as much as 30 percent of angiosperm species. The reorganized earliest Tertiary flora is made up largely of surviving species that assumed new roles of dominance. Persistence of climatically sensitive taxa across the boundary indicates that if paleoclimate was altered by the terminal Cretaceous event, it returned quickly to the pre-event condition.

  14. A calorimetric particle detector using an iridium superconducting phase transition thermometer

    International Nuclear Information System (INIS)

    Frank, M.; Dummer, D.; Cooper, S.; Igalson, J.; Proebst, F.; Seidel, W.

    1994-01-01

    We report on a calorimetric particles detector consisting of an 18.3 g silicon crystal and an iridium superconducting phase transition thermometer. The cryogenic calorimeter and the associated apparatus are described in detail. The pulses from irradiation with an α-particle source have a large unexpected overshoot in addition to the component expected from a naive thermal model. The pulse height spectrum displays an energy resolution of 1 percent FWHM at 6 MeV and good linearity. The noise, electrothermal feedback, and position dependence are discussed. (orig.)

  15. Solid-state electrochromic cell with anodic iridium oxide film electrodes

    International Nuclear Information System (INIS)

    Dautremont-Smith, W.C.; Beni, G.; Schiavone, L.M.; Shay, J.L.

    1979-01-01

    A new solid-state electrochromic cell has been fabricated using an anodic iridium oxide film (AIROF) display electrode. The cell has the symmetric sandwich structure AIROFvertical-barNafionvertical-barAIROF, with the Nafion solid electrolyte opacified by an in situ precipitation technique. A symmetric square-wave voltage of 1.5 V amplitude produces clearly perceivable color changes from pale to dark blue-gray in approx. =1 sec when viewed in diffuse reflection. Good open-circuit optical memory is exhibited:

  16. Chlorido(η4-1,5-cyclooctadiene[(pentafluoroethyldiphenylphosphane]iridium(I

    Directory of Open Access Journals (Sweden)

    Russell G. Baughman

    2011-01-01

    Full Text Available The title structure,[IrCl(C8H12(C14H10F5P], reveals that (C2F5PPh2 (pentafluoroethyldiphenylphosphane or pfepp disrupts the iridium dimer [(codIrCl]2 (cod = cycloocta-1,5-diene by rupturing the bridging chloride ligands and binding in the open coordination site to form (codIr(pfeppCl with the IrI atom in a distorted square-planar coordination environment. The structure deviates very little from the IrI–triphenylphosphine analog, although a significantly (∼20σ shorter Ir—P bond is noted for the title compound.

  17. Enantioselective small molecule synthesis by carbon dioxide fixation using a dual Brønsted acid/base organocatalyst.

    Science.gov (United States)

    Vara, Brandon A; Struble, Thomas J; Wang, Weiwei; Dobish, Mark C; Johnston, Jeffrey N

    2015-06-17

    Carbon dioxide exhibits many of the qualities of an ideal reagent: it is nontoxic, plentiful, and inexpensive. Unlike other gaseous reagents, however, it has found limited use in enantioselective synthesis. Moreover, unprecedented is a tool that merges one of the simplest biological approaches to catalysis-Brønsted acid/base activation-with this abundant reagent. We describe a metal-free small molecule catalyst that achieves the three component reaction between a homoallylic alcohol, carbon dioxide, and an electrophilic source of iodine. Cyclic carbonates are formed enantioselectively.

  18. Exploration of Cocatalyst Effects on a Bimetallic Cobalt Catalyst System: Enhanced Activity and Enantioselectivity in Epoxide Polymerization

    KAUST Repository

    Widger, Peter C. B.; Ahmed, Syud M.; Coates, Geoffrey W.

    2011-01-01

    Organic ionic compounds were synthesized and investigated as cocatalysts with a bimetallic cobalt complex for enantioselective epoxide polymerization. The identities of both the cation and the anion were systematically varied, and the subsequent reactivity was studied. The nature of the ionic cocatalyst dramatically impacted the rate and enantioselectivity of the catalyst system. The ionic cocatalyst [P(N=P(N(CH2)4)3) 4 +][tBuCO2 -] in combination with a bimetallic cobalt complex produced a catalyst system that exhibited the greatest activity and selectivity for a variety of monosubstituted epoxides. © 2011 American Chemical Society.

  19. Exploration of Cocatalyst Effects on a Bimetallic Cobalt Catalyst System: Enhanced Activity and Enantioselectivity in Epoxide Polymerization

    KAUST Repository

    Widger, Peter C. B.

    2011-07-26

    Organic ionic compounds were synthesized and investigated as cocatalysts with a bimetallic cobalt complex for enantioselective epoxide polymerization. The identities of both the cation and the anion were systematically varied, and the subsequent reactivity was studied. The nature of the ionic cocatalyst dramatically impacted the rate and enantioselectivity of the catalyst system. The ionic cocatalyst [P(N=P(N(CH2)4)3) 4 +][tBuCO2 -] in combination with a bimetallic cobalt complex produced a catalyst system that exhibited the greatest activity and selectivity for a variety of monosubstituted epoxides. © 2011 American Chemical Society.

  20. Hydroxynitrile Lyases with α/β-Hydrolase Fold: Two Enzymes with Almost Identical 3D Structures but Opposite Enantioselectivities and Different Reaction Mechanisms

    Science.gov (United States)

    Andexer, Jennifer N; Staunig, Nicole; Eggert, Thorsten; Kratky, Christoph; Pohl, Martina; Gruber, Karl

    2012-01-01

    Hydroxynitrile lyases (HNLs) catalyze the cleavage of cyanohydrins to yield hydrocyanic acid (HCN) and the respective carbonyl compound and are key enzymes in the process of cyanogenesis in plants. In organic syntheses, HNLs are used as biocatalysts for the formation of enantiopure cyanohydrins. We determined the structure of the recently identified, R-selective HNL from Arabidopsis thaliana (AtHNL) at a crystallographic resolution of 2.5 Å. The structure exhibits an α/β-hydrolase fold, very similar to the homologous, but S-selective, HNL from Hevea brasiliensis (HbHNL). The similarities also extend to the active sites of these enzymes, with a Ser-His-Asp catalytic triad present in all three cases. In order to elucidate the mode of substrate binding and to understand the unexpected opposite enantioselectivity of AtHNL, complexes of the enzyme with both (R)- and (S)-mandelonitrile were modeled using molecular docking simulations. Compared to the complex of HbHNL with (S)-mandelonitrile, the calculations produced an approximate mirror image binding mode of the substrate with the phenyl rings located at very similar positions, but with the cyano groups pointing in opposite directions. A catalytic mechanism for AtHNL is proposed, in which His236 from the catalytic triad acts as a general base and the emerging negative charge on the cyano group is stabilized by main-chain amide groups and an α-helix dipole very similar to α/β-hydrolases. This mechanistic proposal is additionally supported by mutagenesis studies. PMID:22851196

  1. Enatioselective[2+2+2] Cycloaddition as A Synthetic Tool

    Institute of Scientific and Technical Information of China (English)

    T.Shibata; S.Yoshida; M.Otsuka; Y.Arai; K.Endo

    2007-01-01

    1 Results Transition metal-catalyzed [2+2+2] cycloaddition is one of the most efficient protocols for the construction of six-membered ring system.Our group has comprehensively studied various types of highly enantioselective [2+2+2] cycloaddition for the synthesis of chiral cycloadducts; we already reported an iridium-catalyzed intermolecular [2+2+2] cycloaddition between α,ω-diynes,having various tethers and substituents on the alkyne termini,and monoalkynes,possessing oxygen or/and nitrogen functiona...

  2. Oxidation of iridium coating on rhenium coated graphite at elevated temperature in stagnated air

    International Nuclear Information System (INIS)

    Huang, Yongle; Bai, Shuxin; Zhang, Hong; Ye, Yicong

    2015-01-01

    Highlights: • Continuous and dense Ir coatings were prepared on graphite by electrodepostion. • The purification of the as-prepared Ir coating was higher than about 99.98%. • The Ir/Re/C specimen kept integrity without significant failures after oxidation. • The average oxidation rate of the Ir coating was about 0.219 mg/(cm 2 min). • Penetrating holes at gains boundaries resulted in the failure of the Ir coating. - Abstract: Continuous and dense iridium coatings were prepared on the rhenium coated graphite specimens by electrodeposition. The iridium/rhenium coated graphite (Ir/Re/C) specimens were oxidized at elevated temperatures in stagnated air for 3600 s. The purification of the as-prepared Ir coating was higher than about 99.98% with the main impurity elements Si, Al, Fe and Ru. After oxidation, the Ir/Re/C specimens kept integrity without significant failures and the average oxidation rate was about 0.219 mg/(cm 2 min). Pores were found at the grain boundaries and concentrated to penetrating holes with the growth of Ir grains, which resulted in disastrous failures of the Ir coating

  3. Oxidation of iridium coating on rhenium coated graphite at elevated temperature in stagnated air

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Yongle; Bai, Shuxin, E-mail: NUDT_MSE_501@163.com; Zhang, Hong; Ye, Yicong

    2015-02-15

    Highlights: • Continuous and dense Ir coatings were prepared on graphite by electrodepostion. • The purification of the as-prepared Ir coating was higher than about 99.98%. • The Ir/Re/C specimen kept integrity without significant failures after oxidation. • The average oxidation rate of the Ir coating was about 0.219 mg/(cm{sup 2} min). • Penetrating holes at gains boundaries resulted in the failure of the Ir coating. - Abstract: Continuous and dense iridium coatings were prepared on the rhenium coated graphite specimens by electrodeposition. The iridium/rhenium coated graphite (Ir/Re/C) specimens were oxidized at elevated temperatures in stagnated air for 3600 s. The purification of the as-prepared Ir coating was higher than about 99.98% with the main impurity elements Si, Al, Fe and Ru. After oxidation, the Ir/Re/C specimens kept integrity without significant failures and the average oxidation rate was about 0.219 mg/(cm{sup 2} min). Pores were found at the grain boundaries and concentrated to penetrating holes with the growth of Ir grains, which resulted in disastrous failures of the Ir coating.

  4. Colorimetric and luminescent bifunctional iridium(III) complexes for the sensitive recognition of cyanide ions

    Science.gov (United States)

    Chen, Xiudan; Wang, Huili; Li, Jing; Hu, Wenqin; Li, Mei-Jin

    2017-02-01

    Two new cyclometalated iridium(III) complexes [(ppy)2Irppz]Cl (1) and [(ppy)2Irbppz]Cl (2) (where ppy = 2-phenylpyridine, ppz = 4,7-phenanthrolino-5,6:5,6-pyrazine, bppz = 2.3-di-2-pyridylpyrazine), were designed and synthesized. The structure of [(ppy)2Irppz]Cl was determined by single crystal X-ray diffraction. Their photophysical properties were also studied. This kind of complexes could coordinate with Cu2 +, the photoluminescence (PL) of the complex was quenched, and the color changed from orange-red to green. The forming M-Cu (M: complexes 1 and 2) ensemble could be further utilized as a colorimetric and emission ;turn-on; bifunctional detection for CN-, especially for complex 1-Cu2 + showed a high sensitivity toward CN- with a limit of diction is 97 nM. Importantly, this kind of iridium(III) complexes shows a unique recognition of cyanide ions over other anions which makes it an eligible sensing probe for cyanide ions.

  5. High-Performance Computer Modeling of the Cosmos-Iridium Collision

    Energy Technology Data Exchange (ETDEWEB)

    Olivier, S; Cook, K; Fasenfest, B; Jefferson, D; Jiang, M; Leek, J; Levatin, J; Nikolaev, S; Pertica, A; Phillion, D; Springer, K; De Vries, W

    2009-08-28

    This paper describes the application of a new, integrated modeling and simulation framework, encompassing the space situational awareness (SSA) enterprise, to the recent Cosmos-Iridium collision. This framework is based on a flexible, scalable architecture to enable efficient simulation of the current SSA enterprise, and to accommodate future advancements in SSA systems. In particular, the code is designed to take advantage of massively parallel, high-performance computer systems available, for example, at Lawrence Livermore National Laboratory. We will describe the application of this framework to the recent collision of the Cosmos and Iridium satellites, including (1) detailed hydrodynamic modeling of the satellite collision and resulting debris generation, (2) orbital propagation of the simulated debris and analysis of the increased risk to other satellites (3) calculation of the radar and optical signatures of the simulated debris and modeling of debris detection with space surveillance radar and optical systems (4) determination of simulated debris orbits from modeled space surveillance observations and analysis of the resulting orbital accuracy, (5) comparison of these modeling and simulation results with Space Surveillance Network observations. We will also discuss the use of this integrated modeling and simulation framework to analyze the risks and consequences of future satellite collisions and to assess strategies for mitigating or avoiding future incidents, including the addition of new sensor systems, used in conjunction with the Space Surveillance Network, for improving space situational awareness.

  6. Detection of triglyceride using an iridium nano-particle catalyst based amperometric biosensor.

    Science.gov (United States)

    Liao, Wei-Yin; Liu, Chung-Chiun; Chou, Tse-Chuan

    2008-12-01

    The detection and quantification of triglyceride (TG) using an iridium nano-particle modified carbon based biosensor was successfully carried out in this study. The detection procedures were based on the electrochemical detection of enzymatically produced NADH. TG was hydrolyzed by lipase and the glycerol produced was catalytically oxidized by NAD-dependent glycerol dehydrogenase producing NADH in a solution containing NAD(+). Glyceryl tributyrate, a short chain triglyceride, was chosen as the substrate for the evaluation of this TG biosensor in bovine serum and human serum. A linear response to glyceryl tributyrate in the concentration range of 0 to 10 mM and a sensitivity of 7.5 nA mM(-1) in bovine serum and 7.0 nA mM(-1) in human serum were observed experimentally. The potential interference of species such as uric acid (UA) and ascorbic acid (AA) was assessed. The incorporation of a selected surfactant and an increase in the incubation temperature appeared to enhance the performance of this biosensor. The conditions for the determination of TG levels in bovine serum using this biosensor were optimized, with sunflower seed oil being used as an analyte to simulate the detection of TG in blood. The experimental results demonstrated that this iridium nano-particle modified working electrode based biosensor provided a relatively simple means for the accurate determination of TG in serum.

  7. Thermal hydraulic modelling of the Mo and Iridium irradiation facilities of the RA10 reactor

    International Nuclear Information System (INIS)

    Gramajo, M.; García, J.; Marcel, C.P.

    2013-01-01

    The RA-10 reactor is a multipurpose, open pool research reactor. The core consists of a rectangular array of MTR type fuel. The produced thermal power is 30 MW which is extracted by the refrigeration system via an ascendant flow through the core. The core reflector is D 2 O contained in a watertight tank. The design of the reactor includes a number of out-core facilities which are meant to be used for industrial, medical and research purposes. Among all the facilities, the most important ones are the Molybdenum and Iridium ones which we modeled in this work. During the normal operation of the reactor, the manipulation and the on-line extraction of the irradiation facilities is foreseen. Therefore the study of the head loss during the normal operation as well as during the extraction maneuvers plays a relevant role in the design and safety analysis. In this work a CFD commercial code is use dto perform the calculations needed to guarantee the design requirements.In addition, a full detailed geometric model for both, the Molybdenum and Iridium facilities,is used to perform the required simulations. The obtained results allow to evaluating the thermal-hydraulic performance of the proposed facilities designs. (author)

  8. Adsorption and desorption of hydrogen and carbon monoxide were studied on alumina-supported iridium catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Etherton, B.P.

    1980-01-01

    The adsorption and desorption of hydrogen and carbon monoxide were studied on alumina-supported iridium catalysts which were examined by a scanning transmission electron microscope (STEM). The metal particle size and number of particles per area of catalyst increased with increasing metal loading. The particles were approx. 10 A. in diameter, cubo-octahedral shaped, and approx. 80-90% disperse. The STEM electron beam caused negligible damage to the samples. Hydrogen adsorption measurements showed that the hydrogen-iridium atom ratio was 1.2:1-1.3:1 and increased with decreasing metal loading. Temperature-programed desorption showed four types of adsorbed hydrogen desorbing at -90/sup 0/C (I), 15/sup 0/C (IV), 115/sup 0/C (II), and 245/sup 0/C (III). Types II and IV desorb from single atom sites and Types I and III from multiple atom sites. Type I is in rapid equilibrium with the gas phase. All desorption processes appear to be first order. Carbon monoxide adsorbed nondissociatively at 25/sup 0/C with approx. 0.7:1 CO/Ir atom ratio. It adsorbed primarily in linear forms at low coverage, but a bridged form appeared at high coverage.

  9. Adsorption and the initial stages of samarium condensation on iridium coated by graphite monolayer

    International Nuclear Information System (INIS)

    Abdullaev, R.M.; Tontegode, A.Ya.; Yusifov, F.K.

    1978-01-01

    Adsorption and the initial stages of vacuum samarium condensation on iridium coated by graphite monolayer (valent-saturated neutral substrate) were studied by the thermodesorption mass-spectrometry and thermoemission methods, and were compared with samarium adsorption and condensation on iridium. Desorption heat of samarium atoms with thin coating of Ir-C, equal to E approximately 1.9 eV has been determined. For desorption with Ir E is approximately 6 eV. Such a great difference in desorption heats is connected with the reduction of covalent constituent of adsorption bond in a neutral substrate. Samarium on Ir-C is found to be condensated in two states: loosely bound and tightly bound which sharply differ in properties. The tightly bound state is characterized by abnormally low vapour pressure. Possible nature of this state is discussed. Double effect on the condensation of the substrate valent saturation is noted. On the one hand, the reduction of the particle bond with the substrate decreases their concentration on the surface, preventing condensation. On the other hand, the release of the valent eloctrons of adatous brings about strong lateral interaction between them, which in its turn, promotes condensation during eased migration on the neutral substrate

  10. Earth Radiation Imbalance from a Constellation of 66 Iridium Satellites: Technological Aspects

    Science.gov (United States)

    Wiscombe, W.; Chiu, C. J-Y.

    2012-01-01

    Iridium Communications Inc. is launching a new generation of polar orbiting communication satellites in 2015-2017. Iridium will provide a hosted payload bay on each of the 66 satellites (plus 6 in-space spares). This offers the potential for a paradigm shift in the way we measure Earth radiation imbalance from space, as well as massive cost savings. Because the constellation provides 24/7 global coverage, there is no need to account for diurnal cycle via extrapolations from uncalibrated narrowband geostationary imagers. And the spares can be rolled over to view the Sun and deep space, then transfer their calibration to the other members of the constellation during the frequent cross-overs. In part using simulations of the constellation viewing realistic Earth scenes, this presentation will address the technological aspects of such a constellation: (1) the calibration strategy; (2) the highly-accurate and stable radiometers for measuring outgoing flux; and (3) the GRACE-inspired algorithms for representing the outgoing flux field in spherical harmonics and thus achieving rv500-km spatial resolution and two-hour temporal resolution.

  11. Efficiency Control in Iridium Complex-Based Phosphorescent Light-Emitting Diodes

    Directory of Open Access Journals (Sweden)

    Boucar Diouf

    2012-01-01

    Full Text Available Key factors to control the efficiency in iridium doped red and green phosphorescent light emitting diodes (PhOLEDs are discussed in this review: exciton confinement, charge trapping, dopant concentration and dopant molecular structure. They are not independent from each other but we attempt to present each of them in a situation where its specific effects are predominant. A good efficiency in PhOLEDs requires the triplet energy of host molecules to be sufficiently high to confine the triplet excitons within the emitting layer (EML. Furthermore, triplet excitons must be retained within the EML and should not drift into the nonradiative levels of the electron or hole transport layer (resp., ETL or HTL; this is achieved by carefully choosing the EML’s adjacent layers. We prove how reducing charge trapping results in higher efficiency in PhOLEDs. We show that there is an ideal concentration for a maximum efficiency of PhOLEDs. Finally, we present the effects of molecular structure on the efficiency of PhOLEDs using red iridium complex dopant with different modifications on the ligand to tune its highest occupied molecular orbital (HOMO and lowest unoccupied molecular orbital (LUMO energies.

  12. Synthesis and green electrophosphorescence of a novel cyclometalated iridium complex in polymer light-emitting diodes

    Energy Technology Data Exchange (ETDEWEB)

    Wu Lilan [Department of Chemistry, National Cheng Kung University, Tainan, Taiwan 70101 (China); Tsai Sunghao [Institute of Electro-Optical Science and Engineering, National Cheng Kung University, Tainan, Taiwan 70101 (China); Guo Tzungfang [Institute of Electro-Optical Science and Engineering, National Cheng Kung University, Tainan, Taiwan 70101 (China); Yang Chenghsien [Carbon Nanocapsules Research Department, Nano-Powder and Thin Film Technology Center, ITRI South, Tainan, Taiwan 709 (China)]. E-mail: jasonyang0606@yahoo.com.tw; Sun, I-W. [Department of Chemistry, National Cheng Kung University, Tainan, Taiwan 70101 (China)]. E-mail: iwsun@mail.ncku.edu.tw

    2007-10-15

    Abstact: In this paper, we synthesized a new complex bis(dibenzo[f,h]quinolinato-N,C {sup 2'}) iridium(III) acetylactonate ((DBQ){sub 2}Ir(acac)) having a longer conjugate system than bis(2-phenylpyridinato-N,C {sup 2'}) iridium(III) acetylacetonate ((PPY){sub 2}Ir(acac)). Interestingly (DBQ){sub 2}Ir(acac) emits at the same wavelength as (photoluminescence of 530 nm) (PPY){sub 2}Ir(acac). A high-efficiency electrophosphorescent polymer light-emitting diodes was constructed by using (DBQ){sub 2}Ir(acac) as the dopant, and a blend of poly(vinylcarbazole) (PVK) with 2-tert-butylphenyl-5-biphenyl-1,3,4-oxadiazol (PBD) as the host material. The electroluminescence efficiency of 9.5 cd/A is reported for the device doped with 3 wt% of (DBQ){sub 2}Ir(acac). In this device, the emission from the PVK or PBD host was effectively inhibited with the using (DBQ){sub 2}Ir(acac) . Emission from the dopant molecules in such devices involve localization of the injected electron and hole on the metal-organic center. This can occur by a variety of mechanisms, including Foerster and Dexter energy transfer from the host transport material to the dopant, and direct trapping of both electrons and holes on the metal-organic center.

  13. PLE CATALYZED HYDROLYZES OF ALPHA-SUBSTITUTED ALPHA-HYDROXY ESTERS - THE INFLUENCE OF THE SUBSTITUENTS

    NARCIS (Netherlands)

    MOORLAG, H; KELLOGG, RM

    1991-01-01

    The enzymatic hydrolyses of a variety of alpha-substituted mandelic and lactic esters using pig liver esterase (PLE) have been investigated. High to moderate enantioselectivity was found for various alpha-substituted mandelic esters, whereas PLE showed low to no enantioselectivity for

  14. A new enantioselective CE method for determination of oxcarbazepine and licarbazepine after fungal biotransformation.

    Science.gov (United States)

    Bocato, Mariana Zuccherato; Bortoleto, Marcela Armelim; Pupo, Mônica Tallarico; de Oliveira, Anderson Rodrigo Moraes

    2014-10-01

    The present work describes, for the first time, the simultaneous separation of oxcarbazepine (OXC) and its active metabolite 10-hydroxy-10,11-dihydrocarbamazepine (licarbazepine, Lic) by chiral CE. The developed method was employed to monitor the enantioselective biotransformation of OXC into its active metabolite by fungi. The electrophoretic separations were performed using 10 mmol/L of a Tris-phosphate buffer solution (pH 2.5) containing 1% w/v of β-CD phosphate sodium salt (P-β-CD) as running electrolyte, -20 kV of applied voltage and a 15°C capillary temperature. The method was linear over the concentration range of 1000-30 000 ng/mL for OXC and 75-900 ng/mL for each Lic enantiomer (r ≥ 0.9952). Within-day precision and accuracy evaluated by RSD and relative errors, respectively, were lower than 15% for all analytes. The validated method was used to evaluate the enantioselective biotransformation of OXC, mediated by fungi, into its active metabolite Lic. This study showed that the fungi Glomerella cingulata (VA1) and Beuveria bassiana were able to enantioselectively metabolize the OXC into Lic after 360 h of incubation. Biotransformation by the fungus Beuveria bassiana showed 79% enantiomeric excess for (S)-(+)-Lic, while VA1 gave an enantiomeric excess of 100% for (S)-(+)-Lic. This study opens a new route to the drug (S)-(+)-licarbazepine. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Muscle invasive bladder cancer treated by transurethral resection, followed by external beam radiation and interstitial iridium-192

    NARCIS (Netherlands)

    A. Wijnmaalen (Arendjan); P.A. Helle (Peter); P.C.M. Koper (Peter); P.P. Jansen (Peter); P. Hanssens (Patrick); C.G.G. Boeken Kruger (Cornelis); W.L.J. van Putten (Wim)

    1997-01-01

    textabstractPurpose: To evaluate the results of transurethral resection (TUR), external beam radiotherapy (EBRT), and interstitial radiation (IRT) with iridium-192, using the afterloading technique in patients with muscle invasive bladder cancer. Methods and Materials: From May 1989 until September

  16. Determination of iridium in the Bering Sea and Arctic Ocean seawaters by anion exchange preconcentration-neutron activation analysis

    International Nuclear Information System (INIS)

    Li Shihong; Mao Xueying; Chai Zhifang

    2004-01-01

    Anion exchange method is investigated to separate and enrich iridium in seawater by radiotracer 192 Ir. The adsorption of Ir in the resin increases with the decreasing acidity in the 0.05-1.2 mol/L HCl media, The recovery of iridium in pH=1.5 seawater reaches 89% by a single anion-exchange column. The polyethylene container of acidity of pH=1.5 are suitable for storing trace Ir in seawater. An anion exchange preconcentration-neutron activation analysis procedure is developed to determine iridium in seawaters sampled from the Bering Sea and Arctic Ocean at different depth. The reagent blank value of the whole procedures is (0.18-0.20) x 10 -12 g Ir. The iridium concentrations in the Bering Sea and Arctic Ocean seawater samples are (0.85-3.58) x 10 -12 g/L (0-3504 m) and (1.26-1.97) x 10 -12 g/L (25-1900 m), respectively

  17. Reversible switching of the sol- gel transition with ultrasound in rhodium(I) and iridium(I) coordination networks

    NARCIS (Netherlands)

    Paulusse, J.M.J.; Beek, van D.J.M.; Sijbesma, R.P.

    2007-01-01

    Reversible coordination networks were prepared by combining diphenylphosphinite telechelic polytetrahydrofuran (2) with [RhCl(COD)]2 or [IrCl(COD)]2 in chloroform. Both systems resulted in stable gels at concentrations above 50 and 30 g/L for the rhodium(I) and iridium(I) networks, respectively. The

  18. Phosphorescence Imaging of Living Cells with Amino Acid-Functionalized Tris(2-phenylpyridine)iridium(III) Complexes

    NARCIS (Netherlands)

    Steunenberg, P.; Ruggi, A.; Berg, van den N.S.; Buckle, T.; Kuil, J.; Leeuwen, van F.W.B.; Velders, A.H.

    2012-01-01

    A series of nine luminescent cyclometalated octahedral iridium(III) tris(2-phenylpyridine) complexes has been synthesized, functionalized with three different amino acids (glycine, alanine, and lysine), on one, two, or all three of the phenylpyridine ligands. All starting complexes and final

  19. Mono and dinuclear iridium, rhodium and ruthenium complexes containing chelating carboxylato pyrazine ligands: Synthesis, molecular structure and electrochemistry

    Czech Academy of Sciences Publication Activity Database

    Govindaswamy, P.; Therrien, B.; Süss-Fink, G.; Štěpnička, P.; Ludvík, Jiří

    2007-01-01

    Roč. 692, č. 8 (2007), s. 1661-1671 ISSN 0022-328X R&D Projects: GA MŠk LC510; GA MŠk(CZ) LC06070 Institutional research plan: CEZ:AV0Z40400503 Keywords : dinuclear complexes * iridium * rhodium * ruthenium * electrochemistry Subject RIV: CG - Electrochemistry Impact factor: 2.168, year: 2007

  20. UV-light promoted C-H bond activation of benzene and fluorobenzenes by an iridium(i) pincer complex.

    Science.gov (United States)

    Hauser, Simone A; Emerson-King, Jack; Habershon, Scott; Chaplin, Adrian B

    2017-03-28

    Iridium(i) carbonyl complex [Ir(2,6-(P t Bu 2 CH 2 ) 2 C 6 H 3 )(CO)] undergoes reversible C-H bond activation of benzene and a series of fluorobenzenes on UV irradiation. Exclusive ortho-selectivity is observed in reactions of fluorobenzene and 1,2-difluorobenzene.

  1. UV-light promoted C–H bond activation of benzene and fluorobenzenes by an iridium(i) pincer complex

    OpenAIRE

    Hauser, Simone A.; Emerson-King, Jack; Habershon, Scott; Chaplin, Adrian B.

    2017-01-01

    Iridium(I) carbonyl complex [Ir(2,6-(PtBu2CH2)2C6H3)(CO)] undergoes reversible C–H bond activation of benzene and a series of fluorobenzenes on UV irradiation. Exclusive ortho-selectivity is observed in reactions of fluorobenzene and 1,2-difluorobenzene.\\ud \\ud

  2. Application of 7-azaisatins in enantioselective Morita–Baylis–Hillman reaction

    Directory of Open Access Journals (Sweden)

    Qing He

    2016-02-01

    Full Text Available 7-Azaisatin and 7-azaoxindole skeletons are valuable building blocks in diverse biologically active substances. Here 7-azaisatins turned out to be more efficient electrophiles than the analogous isatins in the enantioselective Morita–Baylis–Hillman (MBH reactions with maleimides using a bifunctional tertiary amine, β-isocupreidine (β-ICD, as the catalyst. This route allows a convenient approach to access multifunctional 3-hydroxy-7-aza-2-oxindoles with high enantiopurity (up to 94% ee. Other types of activated alkenes, such as acrylates and acrolein, could also be efficiently utilized.

  3. Organocatalytic Michael and Friedel–Crafts reactions in enantioselective synthesis of biologically active compounds

    International Nuclear Information System (INIS)

    Maltsev, O V; Beletskaya, Irina P; Zlotin, Sergei G

    2011-01-01

    Recent applications of organocatalytic Michael and Friedel–Crafts reactions in enantioselective synthesis of biologically active compounds: natural products, pharmaceutical agents and plant protection agents are reviewed. The key mechanisms of stereoinduction, types of organocatalysts and reagents used in these reactions are considered. The material is classified according to the type of newly formed bonds incorporating the asymmetric carbon atom, and the information for the most numerous C–C coupling reactions is systematized according to the natures of the electrophile and the nucleophile. The bibliography includes 433 references.

  4. Enantioselective developmental toxicity and immunotoxicity of pyraclofos toward zebrafish (Danio rerio)

    Energy Technology Data Exchange (ETDEWEB)

    Zhuang, Shulin, E-mail: shulin@zju.edu.cn [Institute of Environmental Science, College of Environmental and Resource Sciences, Zhejiang University, Hangzhou 310058 (China); Zhejiang Provincial Key Laboratory of Organic Pollution Process and Control, Hangzhou 310058 (China); Zhang, Zhisheng [Institute of Environmental Science, College of Environmental and Resource Sciences, Zhejiang University, Hangzhou 310058 (China); Zhang, Wenjing; Bao, Lingling [Institute of Environmental Science, College of Environmental and Resource Sciences, Zhejiang University, Hangzhou 310058 (China); Zhejiang Provincial Key Laboratory of Organic Pollution Process and Control, Hangzhou 310058 (China); Xu, Chao, E-mail: chaoxu@zjut.edu.cn [Research Center of Environmental Science, College of Biological and Environmental Engineering, Zhejiang University of Technology, Hangzhou 310032 (China); Zhang, Hu [Institute of Quality and Standard for Agro-products, Zhejiang Academy of Agricultural Sciences, Hangzhou 210021 (China)

    2015-02-15

    Highlights: • Pyraclofos has significant enantioselective aquatic toxicities to zebrafish. • Pyraclofos induces time- and concentration-dependent developmental toxicity and immunotoxicity. • The mRNA level of IL-1β gene was significantly up-regulated by pyraclofos. • Pyraclofos binds potently to IL-1β, potentially affecting IL-1β-dependent proinflammatory signal transduction. • Our in vitro and in silico studies help to understand the molecular basis for aquatic toxicity of pyraclofos. - Abstract: Pyraclofos, a relatively new organophosphorus pesticide, has shown potential ecotoxicities, however, its aquatic toxicity, especially enantioselective aquatic toxicity, remains largely unknown. Using zebrafish (Danio rerio) as a preeminent vertebrate aquatic model, the enantioselective differences in the developmental toxicity and immunotoxicity of pyraclofos were evaluated. Following 96-h exposure, pyraclofos enantiomers exhibited acute toxicity and showed lethal concentration 50 of 2.23 and 3.99 mg/L for (R)-Pyraclofos and (S)-Pyraclofos, respectively. Exposure to pyraclofos caused time- and concentration-dependent malformations such as pericardial edema, yolk sac edema, crooked bodies and hatching during the embryonic development, with markedly higher percentages of malformation at higher concentrations. The concentration-dependent immunotoxicity to zebrafish embryo exposed to low level pyraclofos was induced with significant up-regulation of mRNA levels of immune-related interleukin-1β (IL-1β) gene. (R)-Pyraclofos was consistently more toxic than (S)-Pyraclofos for the acute toxicity, developmental toxicity and immunotoxicity to zebrafish. Molecular dynamics simulations revealed that at the atomic level, (R)-Pyraclofos binds more potently to IL-1β protein than (S)-Pyraclofos. This enantioselective binding is mainly contributed by the distinct binding mode of pyraclofos enantiomers and their electrostatic interactions with IL-1β, which potentially

  5. Enantioselective biotransformation of propranolol to the active metabolite 4-hydroxypropranolol by endophytic fungi

    Directory of Open Access Journals (Sweden)

    Keyller Bastos Borges

    2011-01-01

    Full Text Available The enantioselective biotransformation of propranolol (Prop by the endophytic fungi Phomopsis sp., Glomerella cingulata, Penicillium crustosum, Chaetomium globosum and Aspergillus fumigatus was investigated by studying the kinetics of the aromatic hydroxylation reaction with the formation of 4-hydroxypropranolol (4-OH-Prop. Both Prop enantiomers were consumed by the fungi in the biotransformation process, but the 4-hydroxylation reaction yielded preferentially (--(S-4-OH-Prop. The quantity of metabolites biosynthesized varied slightly among the evaluated endophytic fungi. These results show that all investigated endophytic fungi could be used as biosynthetic tools in biotransformation processes to obtain the enantiomers of 4-OH-Prop.

  6. Enzymatic Kinetic Resolution of 2-Piperidineethanol for the Enantioselective Targeted and Diversity Oriented Synthesis

    Directory of Open Access Journals (Sweden)

    Dario Perdicchia

    2015-12-01

    Full Text Available 2-Piperidineethanol (1 and its corresponding N-protected aldehyde (2 were used for the synthesis of several natural and synthetic compounds. The existence of a stereocenter at position 2 of the piperidine skeleton and the presence of an easily-functionalized group, such as the alcohol, set 1 as a valuable starting material for enantioselective synthesis. Herein, are presented both synthetic and enzymatic methods for the resolution of the racemic 1, as well as an overview of synthesized natural products starting from the enantiopure 1.

  7. Diastereoselective and enantioselective conjugate addition reactions utilizing α,β-unsaturated amides and lactams

    Directory of Open Access Journals (Sweden)

    Katherine M. Byrd

    2015-04-01

    Full Text Available The conjugate addition reaction has been a useful tool in the formation of carbon–carbon bonds. The utility of this reaction has been demonstrated in the synthesis of many natural products, materials, and pharmacological agents. In the last three decades, there has been a significant increase in the development of asymmetric variants of this reaction. Unfortunately, conjugate addition reactions using α,β-unsaturated amides and lactams remain underdeveloped due to their inherently low reactivity. This review highlights the work that has been done on both diastereoselective and enantioselective conjugate addition reactions utilizing α,β-unsaturated amides and lactams.

  8. Enantioselective developmental toxicity and immunotoxicity of pyraclofos toward zebrafish (Danio rerio)

    International Nuclear Information System (INIS)

    Zhuang, Shulin; Zhang, Zhisheng; Zhang, Wenjing; Bao, Lingling; Xu, Chao; Zhang, Hu

    2015-01-01

    Highlights: • Pyraclofos has significant enantioselective aquatic toxicities to zebrafish. • Pyraclofos induces time- and concentration-dependent developmental toxicity and immunotoxicity. • The mRNA level of IL-1β gene was significantly up-regulated by pyraclofos. • Pyraclofos binds potently to IL-1β, potentially affecting IL-1β-dependent proinflammatory signal transduction. • Our in vitro and in silico studies help to understand the molecular basis for aquatic toxicity of pyraclofos. - Abstract: Pyraclofos, a relatively new organophosphorus pesticide, has shown potential ecotoxicities, however, its aquatic toxicity, especially enantioselective aquatic toxicity, remains largely unknown. Using zebrafish (Danio rerio) as a preeminent vertebrate aquatic model, the enantioselective differences in the developmental toxicity and immunotoxicity of pyraclofos were evaluated. Following 96-h exposure, pyraclofos enantiomers exhibited acute toxicity and showed lethal concentration 50 of 2.23 and 3.99 mg/L for (R)-Pyraclofos and (S)-Pyraclofos, respectively. Exposure to pyraclofos caused time- and concentration-dependent malformations such as pericardial edema, yolk sac edema, crooked bodies and hatching during the embryonic development, with markedly higher percentages of malformation at higher concentrations. The concentration-dependent immunotoxicity to zebrafish embryo exposed to low level pyraclofos was induced with significant up-regulation of mRNA levels of immune-related interleukin-1β (IL-1β) gene. (R)-Pyraclofos was consistently more toxic than (S)-Pyraclofos for the acute toxicity, developmental toxicity and immunotoxicity to zebrafish. Molecular dynamics simulations revealed that at the atomic level, (R)-Pyraclofos binds more potently to IL-1β protein than (S)-Pyraclofos. This enantioselective binding is mainly contributed by the distinct binding mode of pyraclofos enantiomers and their electrostatic interactions with IL-1β, which potentially

  9. Activation of lipase from .I.Geotrichum candidum./I. and its enantioselectivity towards xenobiotic substrates

    Czech Academy of Sciences Publication Activity Database

    Kejík, Z.; Zarevúcka, Marie; Demnerová, K.

    2003-01-01

    Roč. 97, č. 5 (2003), s. 293-294 ISSN 0009-2770. [Sigma-Aldrich konference mladých chemiků, biochemiků a molekulárních biologů /3./. 04.06.2003-07.06.2003, Devět skal - Žďárské vrchy] R&D Projects: GA MŠk OC D13.10 Institutional research plan: CEZ:AV0Z4055905 Keywords : lipase * enantioselectivity Subject RIV: CC - Organic Chemistry

  10. The effect of surface depletion on the work function of arc-melted dilute solution tungsten-iridium alloys

    International Nuclear Information System (INIS)

    D'Cruz, L.A.; Bosch, D.R.; Jacobson, D.L.

    1991-01-01

    The requirements of thermionic electrode materials have emphasized the need for substantial improvements in microstructural stability, strength, and creep resistance at service temperature in excess of 2,500K. The present work extends an earlier study of the effective work function trends of a series of dilute solution tungsten, iridium alloys with iridium contents of 1, 3, and 5 wt%. Since the lifetime of candidate electrode materials is an important consideration, the present work attempts to evaluate the repeatability of the work function trends in these alloys. The effective work function was obtained from measurements of the current emitted from the electrode surface under UHV conditions in the temperature range of 1,800-2,500K using a Vacuum Emission Vehicle (VEV). The data generated in this work have been compared with data obtained in earlier studies performed on these alloys. It was found that the magnitude of the effective work function of these alloys was affected by changes in the subsurface iridium concentration. Furthermore, these alloys exhibited a dependence of the work function on temperature, after prolonged exposure to elevated temperatures. Such a temperature dependence can be explained by diffusion-controlled changes in the coverage of an iridium monolayer on the surface. It is proposed that the significant difference in effective work function trends obtained after prolonged exposure to elevated temperatures is a direct consequence of changes in the coverage of an iridium-rich monolayer on the electrode surface. The constitution of such a surface layer, however, would be governed by composition changes in the subsurface regions of the electrode caused thermally-activated transport processes

  11. Ir-catalyzed C-H silylations of phenyldeazapurines

    Czech Academy of Sciences Publication Activity Database

    Sabat, Nazarii; Poštová Slavětínská, Lenka; Hocek, Michal

    2015-01-01

    Roč. 56, č. 49 (2015), s. 6860-6862 ISSN 0040-4039 Institutional support: RVO:61388963 Keywords : C-H silylation * deazapurines * iridium catalysis * C-H activations Subject RIV: CC - Organic Chemistry Impact factor: 2.347, year: 2015

  12. Iridium-catalyzed direct synthesis of tryptamine derivatives from indoles: exploiting n-protected β-amino alcohols as alkylating agents.

    Science.gov (United States)

    Bartolucci, Silvia; Mari, Michele; Bedini, Annalida; Piersanti, Giovanni; Spadoni, Gilberto

    2015-03-20

    The selective C3-alkylation of indoles with N-protected ethanolamines involving the "borrowing hydrogen" strategy is described. This method provides convenient and sustainable access to several tryptamine derivatives.

  13. Enantioselective copper-catalysed propargylic substitution: synthetic scope study and application in formal total syntheses of (+)-anisomycin and (-)-cytoxazone

    NARCIS (Netherlands)

    Detz, R.J.; Abiri, Z.; le Griel, R.; Hiemstra, H.; van Maarseveen, J.H.

    2011-01-01

    A copper catalyst with a chiral pyridine-2,6-bisoxazoline (pybox) ligand was used to convert a variety of propargylic esters with different side chains (R=Ar, Bn, alkyl) into their amine counterparts in very high yields and with good enantioselectivities (up to 90 % enantiomeric excess (ee)).

  14. Chiral separation of substituted phenylalanine analogues using chiral palladium phosphine complexes with enantioselective liquid-liquid extraction

    NARCIS (Netherlands)

    Verkuijl, B.J.V.; Schuur, B.; Minnaard, A.J.; Vries, de J.G.; Feringa, B.L.

    2010-01-01

    Chiral palladium phosphine complexes have been employed in the chiral separation of amino acids and phenylalanine analogues in particular. The use of (S)-xylyl-BINAP as a ligand for the palladium complex in enantioselective liquid–liquid extraction allowed the separation of the phenylalanine

  15. Enantioselective Effects of o,p'-DDT on Cell Invasion and Adhesion of Breast Cancer Cells: Chirality in Cancer Development.

    Science.gov (United States)

    He, Xiangming; Dong, Xiaowu; Zou, Dehong; Yu, Yang; Fang, Qunying; Zhang, Quan; Zhao, Meirong

    2015-08-18

    The o,p'-dichlorodiphenyltrichloroethane (DDT) with a chiral center possesses enantioselective estrogenic activity, in which R-(-)-o,p'-DDT exerts a more potent estrogenic effect than S-(+)-o,p'-DDT. Although concern regarding DDT exposure and breast cancer has increased in recent decades, the mode of enantioselective action of o,p'-DDT in breast cancer development is still unknown. Herein, we conducted a systematic study of the effect of o,p'-DDT on stereoselective breast tumor cell progression in a widely used in vitro breast tumor cell model, MCF-7 cells. We demonstrated that R-(-)-o,p'-DDT promoted more cancer cell invasion mediated by the human estrogen receptor (ER) by inducing invasion-promoted genes (matrix metalloproteinase-2 and -9 and human telomerase reverse transcriptase) and inhibiting invasion-inhibited genes (tissue inhibitor of metalloproteinase-1 and -4). Molecular docking verified that the binding affinity between R-(-)-o,p'-DDT and human ER was stronger than that of S-(+)-o,p'-DDT. The enantioselective-induced decrease in cell-to-cell adhesion may involve the downregulation of adhesion-promoted genes (E-cadherin and β-catenin). For the first time, these results reveal that estrogenic-like chiral compounds are of significant concern in the progression of human cancers and that human health risk assessment of chiral chemicals should consider enantioselectivity.

  16. Proof of concept for continuous enantioselective liquid-liquid extraction in capillary microreactors using 1-octanol as a sustainable solvent

    NARCIS (Netherlands)

    Susanti, S.; Meinds, Tim G.; Pinxterhuis, Erik B.; Schuur, Boelo; De Vries, Johannes G.; Feringa, Ben L.; Winkelman, Jozef G.M.; Yue, Jun; Heeres, Hero J.

    2017-01-01

    The use of capillary microreactors for enantioselective liquid-liquid extraction (ELLE) was successfully demonstrated using a model system consisting of a buffered aqueous amino acid derivative (3,5-dinitrobenzoyl-(R,S)-leucine) solution (phosphate buffer, pH 6.58) and a chiral cinchona alkaloid

  17. A Convergent Enantioselective Total Synthesis of (-)-Perhydrohistrionicotoxin with an Intramolecular Imino Ene-type Reaction as a Key Step

    DEFF Research Database (Denmark)

    Tanner, David Ackland; Hagberg, Lars

    1998-01-01

    A convergent enantioselective total synthesis of the neurotoxic spirocyclic alkaloid (-)-perhydrohistrionicotoxin (2) is described. A Lewis acid-mediated intramolecular imine ene-type reaction was used for the key spirocyclisation step (14 to 3, with 3 being obtained as a single diastereoisomer...

  18. Organocatalytic Enantioselective Pictet-Spengler Approach to Biologically Relevant 1-Benzyl-1,2,3,4-Tetrahydroisoquinoline Alkaloids

    NARCIS (Netherlands)

    Ruiz-Olalla, A.; Würdemann, M.A.; Wanner, M.J.; Ingemann, S.; van Maarseveen, J.H.; Hiemstra, H.

    2015-01-01

    A general procedure for the synthesis of 1-benzyl-1,2,3,4-tetrahydroisoquinolines was developed, based on organocatalytic, regio- and enantioselective Pictet-Spengler reactions (86-92% ee) of N-(o-nitrophenylsulfenyl)-2-arylethyl-amines with arylacetaldehydes. The presence of the

  19. DNA-Accelerated Copper Catalysis of Friedel-Crafts Conjugate Addition/Enantioselective Protonation Reactions in Water

    NARCIS (Netherlands)

    García-Fernández, Almudena; Megens, Rik P.; Villarino, Lara; Roelfes, Gerard

    2016-01-01

    DNA-induced rate acceleration has been identified as one of the key elements for the success of the DNA-based catalysis concept. Here we report on a novel DNA-based catalytic Friedel-Crafts conjugate addition/enantioselective protonation reaction in water, which represents the first example of a

  20. Paralogous gene analysis reveals a highly enantioselective 1,2-O-isopropylideneglycerol caprylate esterase of Bacillus subtilis

    NARCIS (Netherlands)

    Droge, MJ; Bos, R; Quax, WJ

    Carboxylesterase NP of Bacillus subtilis Thai 1-8, characterized in 1992 as a very enantioselective (S)-naproxen esterase, was found to show no enantiopreference towards (S)-1,2-O-isopropylideneglycerol (IPG) esters. The ybfK gene was identified by the B. subtilis genome project as an unknown gene