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1994 Fiscal Year Final Research Report Summary

Mechanism of Stereocontrol in Multi-step reaction

Research Project

Project/Area Number 04403006
Research Category

Grant-in-Aid for General Scientific Research (A)

Allocation TypeSingle-year Grants
Research Field 有機化学一般
Research InstitutionKYOTO UNIVERSITY

Principal Investigator

OHNO Atsuyoshi  Inst.Chem.Res., Kyoto Univ., 化学研究所, 教授 (70027077)

Co-Investigator(Kenkyū-buntansha) OKAMURA Mutsuo  Fac.Sci., Niigata Uoiv., 理学部・化学科, 助教授 (30215503)
HDTA Yasuo  Iost.Chem.Res., Kyoto Univ., 化学研究所, 助教授 (10127277)
KAWAI Yasushi  Inst.Chem.Res., Kyoto Univ., 化学研究所, 助手 (20240830)
Project Period (FY) 1992 – 1994
KeywordsOxidation / Reduction / Awial asymmetry / Carbonyl Group / Sulfinyl Group / Stereospecific / Stereochemistry / NAD (P)^+ Coenzyme
Research Abstract

Mechanism of biologically important (net) hydride transfer from NADH or NADPH to a substrate has been discussed from the viewpoint of physical organic chemistry. It is emphasized that the (net) hydride transfer involves an electron-transfer complex as an intermediate of the reaction. The intermediate plays a crucial role in determining stereochemistry of the reaction. Orientation of dipolar functional group such as carbonyl or sulfinyl selects molecular face to afford the complexation, then defines the face of reaction. Steric balkiness is of the second importance in defining the face of reaction. The mechanism observed is named as nonsteric stereochemistry. Molecular interactions observed in organic reactions and discussed herein is closely related to those in biological reactions.

  • Research Products

    (66 results)

All Other

All Publications (66 results)

  • [Publications] M.Fujii, T.Kamata, M.Okamura, A.Ohno: "A Novel Coenzyme NAD(P)^+-NAD(P)H Model with Axial Chirality.Its Preparation and Stereochemistry" J.Chem.Soc., Chem.Commun.905-906 (1992)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K.Nakamura, S.Takano, K.Terada, A.Ohno: "Asymmetric Reduction of Butyl Pyruvate Catalyzed by Immobilized Glycerol Dehydrogenase in Organic...." Chem.Lett.951-954 (1992)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] M.Okamura, T.Kashiwagi, Y.Mikata, A.Ohno,et: "Stereospecific Electrochemical Oxidation of NAD(P)H Analogs Mediated by Radical Cation of Amines" Chem.Lett.1247-1250 (1992)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] A.Ohno, M.Higaki, M.Okamura: "Further Evidence to Understand the Stereochemistry of the Reactions of α-Sulfinyl Carbanions" Heteroatom Chem.3. 513-519 (1992)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] M.Fujii, K.Kawaguchi, K.Nakamura, A.Ohno: "Stereoselective Synthesis of (±)-Isonitramine and (±)-Sibirine" Chem.Lett.1493-1496 (1992)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] M.Okamura, Y.Mikata, A.Ohno,et al.: "NAD(P)^+-NAD(P)H Models. 81. Temperature-Dependent Stereospecificity in the Interconversion between..." Bull.Chem.Soc.Jpn.66. 1191-1196 (1993)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] M.Okamura, Y.Mikata, A.Ohno,et al.: "NAD(P)^+-OAD(P)H Models. 82.Effect of Mdgnesium Ion on the Stereospecificity and Conformations at the..." Bull.Chem.Soc.Jpn.66. 1197-1203 (1993)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K.Nakamura, S.Kondo, A.Ohno,et al.: "Stereochemical Control in Microbial Reduction.21. Effect of Organic Solvents on Reduction of α-Keto..." Bull.Chem.Soc.Jpn.66. 2738-2743 (1993)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] I.Nakamura, S.Kondo, Y.Kdwai, A.Ohno: "Asymmetric Reduction of Ketopantolactone by Bakers' Yeast" Tetrahedron: Asymmetry. 4. 1253-1254 (1993)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] S.Yasui, K.Shioji, A.Ohno,et al.: "The Arbuzov Reaction of Alkyl Diphenylphosphinites with 10-Methylacridinium IOn.Kinetic Study on..." Bull.Chem.Soc.Jpn.66. 2077-2083 (1993)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] S.Yasui, K.Shioji, A.Ohno,et al.: "The Catalytic Role of Iodide Ion/Iodine Couple in the Photo-Reduction of 10-Methylacridinium Ion with..." Chem.Lett.1393-1396 (1993)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K.Nakamura, S.Takano, A.Ohno: "Diastereoselective Reduction of Ethyl α-Methy1-β-oxobutanoate by Immobilized Geotrichum candidum..." Tetrahedron Lett.34. 6087-6090 (1993)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Y.Kawai, I.Takanobe, A.Ohno,et al.: "Stereoselective Synthesis of Ethyl (2S,3S)-Anti-2-Methyl-3-hydroxybutanoate Mediated by an Oxido..." Tetrahedron Lett.35. 147-148 (1994)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Y.Kawai, M.Tsujimoto, A.Ohno,et al.: "Asymmetric Reduction of β-Keto Esters with an Enzyme from Bakers' Yeast" Bull.Chem.Soc.Jpn.67. 524-528 (1994)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K.Nakamura, S.Kondo, A.Ohno: "Effect of Cyclodextrin on Improvement of Enantioselectivity in the Reduction of Ketopantolactone..." Bioorg.& Med. Chem.2. 433-437 (1994)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] T.Kimura, T.Maruyama, A.Ohno, et al.: "Structural Ejfect on Chelation Selectivity of Alkaline Earth Metal Ions with Aminopolycarboxylate-Type..." Bull.Chem.Soc.Jpn.67. 1615-1621 (1994)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K.Nakamura, M.Kinoshita, A.Ohno et al.: "Effect of Solvent on Lipase-Catalyzed Transesterification in Organic Media" Tetrahedron. 50. 4681-4690 (1994)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Y.Kawai, S.Kondo, A.Ohno,et al.: "Stereochemical Control in Microbial Reduction.23. Thermal Treatment of Bakers' Yeast for Controlling..." Bull.Cmem.Soc.Jpn.67. 2244-2247 (1994)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] S.Yasui, M.Fujii, A.Ohno,et al.: "Mechanism of Dediazoniation of Arenediazonium Salts with Triphenylphosphine and Trialkyl Phosphites...." J.Cmem.Soc., Perkin Trans.2. 177-183 (1994)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K.Nakamura, Y.Inoue, A.Ohno: "Enantioselective Microbial Oxidation of 1-Arylethanol in an Organic Solvent" Tetrahedron Lett.35. 4375-4376 (1994)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] S.Yasui, K.Shioji, A.Ohno: "Reactivity of a Phosphoranyl Radical Generated by Photoreaction of Phenyl Diphenylphosphinite with..." Heteroatom Chem.5. 85-90 (1994)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] S.Yasui, K.Shioji, A.Ohno: "Reaction of a Cation Radical Generated from Trivalent Phosphorus Compound through Single-Electron Transfer..." Tetrahedron Lett.35. 2695-2698 (1994)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] A.Ohno, A.Tsutsumi, Y.Kawai,et al.: "NAD(P)^+-NAD(P)H Models. 83. Molecular Asymmetry with a Carbonyl Group:Electronically Controlled..." J.Am.Chem.Soc.116. 8133-8137 (1994)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] I.Nakamura, M.Kawasake, A.Ohno: "Effects of Substrate on Lipase-Catalyzed Transesterification of ω-Substituted 1-Dlkanols in Organic..." Bull.Chem.Soc.Jpn.67. 3053-3056 (1994)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] M.Uemura, H.Nishimura, A.Ohno,et al.: "Kinetic Resolution of Hydroxymethy1-Substituted (Arene)Cr(CO)_3 and (Diene)Fe(CO)_3 by Lipase" Tetrahedron: Asymmetry. 5. 1673-1682 (1994)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K.Ndiamura, S.Kondo, D.Ohno,er al.: "Purification and Characterization of α-Keto Ester Reductases from Bakers' Yeast" Biosci.Biotech.Biochem.58. 2236-2240 (1994)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] A.Ohno, J.Kunitomo, T.Kawamoto, et al.: "Variation of Reaction Channel in a Flavoenzyme Model with a Modified Pqridine Ring" Tetrahedron Lett.35. 9729-9732 (1994)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] T.Kimura, T.Maruyama, A.Ohno, et al.: "1,2-Bis(ο-aminophenoxy)ethane-N,N,N',N'-tetraacetic acid Derivatives on Complexation with Lanthanoid..." Meteroatom Them.6(in press). (1995)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] A.Ohno, N.Yamazaki, M.Okamura,et al.: "NAD(P)^+-NAD(P)H Models. 84. Stereochemistry Controlled by the Electronic Effect from a Sulfinyl Group" Heteroatom Chem.6(in press). (1995)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] O.Kawai, K.Takaoobe, D.Ohno: "Stereochemical Control in Microbial Reduction.25. Additives Controlling Diastereoselectivity in a..." Bull.Chem.Soc.Jpn.68. 285-288 (1995)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K.Nakamura, O.Inoue, A.Ohno: "Improvement of Enantioselectivity of Microbial Reduction by Using Organic Solvent Redox Coupler..." Tetrahedron Lett.36. 265-266 (1995)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Kawai, K.Hida, A.Ohno,et al.: "Introduction of Plural Asymmetric Centers by a β-Keto Ester Reductase from Bakers' Yeast" Tetrahedron Lett.36. 591-592 (1995)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] I.Nakamura, S.Kondo, D.Ohno,et al.: "Mechanistic Study for Stereochemical Control of Microbial Reduction of α-Keto Esters in an Organic..." Tetrahedron. 51(in press). (1995)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] M.Fujii, T.Kamata, M.Okamura, and A.Ohno: "A Novel Coenzyme NAD (P)^+-NAD (P) H Model with Axial Chirality. Its Preparation and Stereochemistry" J.Cmem.Soc., Chem.Commun.905-906 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K.Ndkamura, S.Takano, K.Terada, and A.Ohno: "Asymmetric Reduction of Butyl Pyruvate Catalyzed by Immobilized Glycerol Dehydrogenase in Organic-Aqueous Biphasic Media" Chem.Lett.951-954 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] M.Okamura, T.Kashiwagi, Y.Mikata, N.Yamazaki, and A.Ohno: "Stereospecific Electrochemical Oxidation of NAD (P) H Analogs Mediated by Radical Cation of Aoilines" Chem.Lett.1247-1250 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] A.Ohno, M.Higaki, and M.Okamura: "Further Evidence to Understand the Stereochemistry of the Reactions of alpha-Sulfinyl Carbanions" Heteroatom Chem.3. 513-519 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] M.Fujii, K.Kawaguchi, K.Nakamura, and A.Ohno: "Stereoselective Synthesis of (<plus-minus>)-Isonitramine and (<plus-minus>)-Sibi " Chem.Lett.1493-1496 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] M.Okamura, Y.Mikata, N.Yamazaki, A.Tsutsumi, and A.Ohno: "NAD (P)^+-NAD (P) H Models. 81. Temperature-Dependent Stereospecificity in the Interconversion between Central and Axial Chiralities" Bull.Chem.Soc.Jpn.66. 1191-1196 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] M.Okamura, Y.Mikata, N.Yamazaki, A.Tsutsumi, and A.Ohno: "NAD (P)^+-NAD (P) H Models. 82. Effect of Magnesium Ion on the Stereospcificity and Conformations at the Ground and Transition States of the Reaction" Bull.Chem.Soc.Jpn.66. 1197-1203 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K.Ndkamura, S.Kondo, Y.Kawai, and A.Ohno: "Stereochemical Control in Microbial Reduction. Effect of Organic Solvents on Reduction of alpha-keto Esters Mediated by Bakers' Yeast" Bull.Chem.Soc.Jpn.66. 2738-2743 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K.Nakamura, S.Kondo, Y.Kawai and A.Ohno: "Asymmetric Reduction of Ketopantolactone by Bakers' Yeast" Tetrahedron : Asymmetry. 4. 1253-1254 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] S.Yasui, K.Shioji, M.Yoshihara, T.Maeshima, and A.Ohno: "The Arbuzov Reaction of Alkyl Diphenylphosphinites with 10-Methylacridinium Ion. Kinetic Study on the Formation and the Decomposition of Phosphonium Intermediates" Bull.Chem.Soc.Jpn.66. 2077-2083 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] S.Yasui, K.Shioji, A.Ohno and M.Yoshihara: "The Catalytic Role of Iodide Ion/Iodine Couple in the Photo-Reduction of 10-Methylacridinium Ion with Diphenylphosphine Oxide" Chem.Lett.1393-1396 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K.Nakamura, S.Takano, and A.Ohno: "Diastereoselective Reduction of Ethyl alpha-Methyl-beta-oxobutanoate by Immobilized Geotrichum candidum in an Organic Solvent" Tetrahedron Lett.34. 2087-6090 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Y.Kawai, K.Takanobe, M.Tsujimoto and A.Ohno: "Stereoselective Synthesis of Ethyl (2S,3S) -Anti-2-Methyl-3-Hydroxybutanoate Mediated by an Oxidoreductase from Geotrichum candidum" Tetrahedron Lett.35. 147-148 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Y.Kawai, M.Tsujimoto, S.Kondo, K.Takanobe, K.Nakamura and A.Ohno: "Asymmetric Reduction of beta-Keto Esters with an enzyme from Bakers' Yeast" Bull.Chem.Soc.Jpn.67. 524-528 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K.Nakamura, S.Kondo and A.Ohno: "Effect of Cyclodextrin on Improvement of Enantio-selectivity in the Reduction of Ketopantolactone with Bakers' Yeast" Bioorg.Med.Chem.2. 433-437 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T.Kimura, T.Maruyama, M.Okamura, T.Sugiyama, T.Ando, and A.Ohno: "Structural Effect on Chelation Selectivity of Alkaline Earth Metal Ions with Aminopolycarboxylate-Type Chelators" Bull.Chem.Soc.Jpn.67. 1615-1621 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K.Nakamura, M.Kinoshita and A.Ohno: "Effect of Solvent on Lipase-Catalyzed Trans-esterification in Organic Media" Tetrahedron. 50. 4681-4690 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Y.Kawai, S.Kondo, M.Tsujimoto, K.Nakmura and A.Ohno: "Stereochemical Control in Microbial Reduction. 23. Thermal Treatment of Bakers' Yeast for Controlling the Stereoselectivity of Reductions" Bull.Chem.Soc.Jpn.67. 2244-2247 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] S.Yasui, M.Fujii, C.Kawano, Y.Nishimura, K.Shioji and A.Ohno: "Mechanism of Dediazoniation of Arenediazonium Salts with Triphenylphosphine and Trialkyl Phosphites. Generation of Cation Radicals from Trivalent Phosphorus Compounds and Their Reactions" J.Chem.Soc., Perkin Trans.2. 177-183 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K.Nakamura, Y.Inoue and A.Ohno: "Enantioselective Microbial Oxidation of 1-Aryl-ethanol in an Organic Solvent" Tetrahedron Lett.35. 4376-5375 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] S.Yasui, K.Shioji and A.Ohno: "Reactivity of a Phosphoranyl Radical Generated by Photoreaction of Phenyl Diphenylphosphinite with 10-Methylacridinium Iodide. alpha-Scission vs. Single Electron Transfer" Heteroatom Chem.5. 85-90 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] S.Yasui, K.Shioji and A.Ohno: "Reaction of a Cation Radical Generated from Trivalent Phosphorus Compound through Single-Electron Transfer to Arenediazonium Salt" Tetrahedron Lett.35. 2695-2698 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] A.Ohno, A.Tsutsumi, Y.Kawai, N.Yamazaki, Y.Mikata and M.Okamoto: "NAD (P)^+-NAD (P) H Models. 83. Molecular Asymmetry with a Chiral Group : electronically Controlled Stereo-chemistry in the Reaction of NAD (P)^+/NAD (P) H Analogs" J.Am.Chem.Soc.116. 8133-8137 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] I.Nakamura, M.Kawai, and A.Ohno: "Effects of Substrate Structure on Lipase-Catalyzed Transesterification of omega-Substituted 1-Alkanols in Organic Solvents" Bull.Chem.Soc.Jpn.67. 3053-3056 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] M.Uemura, H.Nishimura, S.Yamada, Y.Hayashi, K.Nakamura, K.Ishihara, and A.Ohno: "Kinetic Resolution of Hydroxymethyl-Substituted (Arene) Cr (CO)_3 and (Diene) Fe (CO)_3 by Lipase" Tetrahedron : Asymmetry. 5. 1673-1682 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K.Nakamura, S.Kondo, Y.Kawai, N.Nakajima and A.Ohno: "Purification and Characterization of alpha-Keto Ester Reductase from Bakers" Yeast" Biosci.Biotech.Biochem.58. 2236-2240 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] A.Ohno, J.Kunitomo, T.Kawamoto, M.Tomishima, K.Bessho, and F.Yoneda: "Variation of Reaction Channel in a Flavoenzyme Model with a Modified Pyrimidine Ring" Tetrahedron Lett.35. 9729-9732 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T.Kimura, T.Maruyama, M.Okamura, T.Sugiyama, T.Ando and A.Ohno: "1,2-Bis (omicron-aminophenoxy) ethane-N,N,N', N'-tetraacetic Acid Derivatives on Complexation with Lanthanoid Metal Ions. Correlation between Size of Trapping Hole and Metal Ion" Heteroatom Chem.(in press). (1995)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] A.Ohno, N.Yamazaki, A.Tsutsumi, Y.Mikata and M.Okamoto: "NAD (P)^+-NAD (P) H Models. 84. Stereochemistry Controlled by the Electronic Effect from a Sulfinyl Group" Heteroatom Chem.(in press). (1995)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Y.Kawai, K.Takanobe and A.Ohno: "Stereochemical Tontrol in Microbial Reduction. 25. Additives Controlling Diastereoselectivity in a Microbial Reduction of Ethyl 2-Methyl-3-oxobutanoate" Bull.Chem.Soc.Jpn.68. 285-288 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K.Nakamura, Y.Inoue and A.Ohno: "Improvement of Enantioselectivity of Microbial Reduction by Using Orgnaic Solvent Redox Coupler System" Tetrahedron Lett.36. 265-266 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Y.Kawai, K.Hida, K.Nakamura and A.Ohno: "Introduction of Plural Asymmetric Centers by a beta-Keto Ester Reductase from Bakers' Yeast" Tetrahedron Lett.36. 591-592 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K,Nakamura, S.Kondo, N.Nakajima and A.Ohno: "Mechanistic Study for Stereochemical Control of Microbial Reduction of alpha-Keto Esters in an Orgnaic Solvent" Tetrahedron. (in press). (1995)

    • Description
      「研究成果報告書概要(欧文)」より

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Published: 1996-04-15  

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