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Asymmetric Synthesis Catalyzed by Transition-Metal Complexes

Research Project

Project/Area Number 05234101
Research Category

Grant-in-Aid for Scientific Research on Priority Areas

Allocation TypeSingle-year Grants
Research InstitutionKyoto University (1994-1996)
Hokkaido University (1993)

Principal Investigator

HAYASHI Tamio  Kyoto University, Graduate School of Science, Professor, 大学院・理学研究科, 教授 (00093295)

Co-Investigator(Kenkyū-buntansha) HIYAMA Tamejiro  Tokyo Institute of Technology, Research Laboratory of Resources Utilization, Pro, 資源化学研究所, 教授 (90026295)
SHIBASAKI Masakatsu  University of Tokyo, Faculty of Pharmaceutical Sciences, Professor, 薬学部, 教授 (30112767)
KITAMURA Masato  Nagoya University, Graduate School of Science, Associate Professor, 大学院・理学研究科, 助教授 (50169885)
KATSUKI Tsutomu  Kyushu University, Faculty of Science, Professor, 理学部, 教授 (40037271)
Project Period (FY) 1993 – 1995
Project Status Completed (Fiscal Year 1996)
Budget Amount *help
¥79,000,000 (Direct Cost: ¥79,000,000)
Fiscal Year 1995: ¥31,000,000 (Direct Cost: ¥31,000,000)
Fiscal Year 1994: ¥26,600,000 (Direct Cost: ¥26,600,000)
Fiscal Year 1993: ¥21,400,000 (Direct Cost: ¥21,400,000)
KeywordsCatalytic Asymmetric Synthesis / Transition-Metal Catalyst / Asymmetric Hydrogenation / Asymmetric Oxidation / Asymmetric Hydrosilylation / Asymmetric Aldol Reaction / Asymmetric Coupling
Research Abstract

Among various types of asymmetric reactions, reaction with a chiral catalyst is obviously the best choice, because the catalytic asymmetric synthesis requires ideally only one molecule of a chiral catalyst in order to produce a large quantity of an optically active substance. During 1993-1995, we developed new chiral transition-metal catalysts and used them successfully for several types of catalytic asymmetric reactions including asymmetric carbon-carbon bond forming reactions. The examples are : 1) Asymmetric hydrosilylation of olefins catalyzed by a palladium complex coordinated with new monodentate phosphine ligand MOP.2) Asymmetric epoxidation of olefins with new salen-manganese catalysts. 3) Asymmetric nitro-aldol reactions catalyzed by hetero-bimetallic systems.

Report

(4 results)
  • 1996 Final Research Report Summary
  • 1995 Annual Research Report
  • 1994 Annual Research Report
  • 1993 Annual Research Report
  • Research Products

    (32 results)

All Other

All Publications (32 results)

  • [Publications] T.Hayashi: "Enantioposition-Selective Alkynylation of Biaryl Ditriflates by Palladium-Catalyzed Asymmetric Cross-Coupling" Tetrahedron Lett.37. 3161-3164 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] T.Hayashi: "Asymmetric Hydrosilylation of Cyclic 1,3-Dienes Catalyzed by an Axially Chiral Monophosphine-Palladium Complex" Tetrahedron Lett.37. 4169-4172 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] T.Hayashi: "Catalytic Asymmetric Synthesis of Optically Active Olefins by Palladium-Catalysed Asymmetric Reduction of Racemic Allylic Esters with Formic Acid" Chem.Commun.1767-1768 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] T.Katsuki: "Enantioselective Epoxidation of 2,2-Dimethylchromenes Using Achiral Mn-Salen Complex as a Catalyst in the Presence of Chiral Amine" Synlett. 1079-1081 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] M.Shibasaki: "Asymmetric Heck Reaction-Carbanion Capture Process.Catalytic Asymmetric Total Synthesis of(-)-Δ^<9(12)>-Capnellene" J.Am.Chem.Soc.118. 7108-7116 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] M.Shibasaki: "Catalytic Asymmetric Synthesis of α-Hydroxy Phosphonates Using the Al-Li-BINOL Complex" J.Org.Chem.61. 2926-2927 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] T.Hayashi: "Enantioposition-Selective Alkynylation of Biaryl Ditriflates by Palladium-Catalyzed Asymmetric Cross-Coupling" Tetrahedron Lett.37. 3161-3164 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] T.Hayashi: "Asymmetric Hydrosilylation of Cyclic 1,3-Dienes Catalyzed by an Axially Chiral Monophosphine-Palladium Complex" Tetrahedron Lett.37. 4169-4172 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] T.Hayashi: "Catalytic Asymmetric Synthesis of Optically Active Olefins by Palladium-Catalysed Asymmetric Reduction of Racemic Allylic Esters with Formic Acid" J.Chem.Soc., Chem.Commun.1767-1768 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] T.Katsuki: "Enantioselective Epoxidation of 2,2-Dimethylchromenes Using Achiral Mn-Salen Complex as a Catalyst in the Presence of Chiral Amine" Synlett. 1079-1081 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] M.Shibasaki: "Asymmetric Heck Reaction-Carbanion Capture Process. Catalytic Asymmetric Total Synthesis of (-) -DELTA^9 (12) -Capnellene" J.Am.Chem.Soc.118. 7108-7116 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] M.Shibasaki: "Catalytic Asymmetric Synthesis of alpha-Hydroxy Phosphonates Using the Al-Li-BINOL Complex" J.Org.Chem.61. 2926-2927 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] 林民生: "Catalytic Asymmetric Synthesis of Axially Chiral Biaryls by Palladium-Catalyzed Enantioposition-Selective Cross-Coupling" J.Am.Chem.Soc.117. 9101-9102 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] 濱田哲也: "Mechanism of One Oxygen Atom Transfer from Oxo(Salen)manganese(V)Complex to Olefins" Tetrahedron. 52. 515-530 (1996)

    • Related Report
      1995 Annual Research Report
  • [Publications] 北村雅人: "Asymmetric Hydrogenation of β-Keto Phosphonates:A Practical Way to Fosfomycin" J.Am.Chem.Soc.117. 2931-2932 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] 笹井宏明: "The First Heterobimetallic Multifunctional Asymmetric Catalyst" J.Am.Chem.Soc.117. 6194-6198 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] 荒井孝義: "A New Multifunctional Heterobimetallic Asymmetric Catalyst for Michael Additions and Tandem Michael-Aldol Reactions" Angew.Chem.Int.Ed.Engl.35. 104-106 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] 大村英明: "Catalytic Asymmetric Hydrosilylation of 1,3-Dienes with Difluoro(phenyl)silane" J.Organomet.Chem.499. 167-171 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] 林民生: "Ferrocenes" VCH Verlagsgesellshaft, 1-540 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] 林 民生: "Catalytic Asymmetric Reduction of Allylic Esters with Formic Acid Catalyzed by Palladium-MOP Complexes" J. Am. Chem. Soc.116. 775-776 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] 林 民生: "Optically Active Ruthenocenylbisphosphines: New Efficient Chiral Phosphine Ligands for Catalytic Asymmetric Reactions" J. Am. Chem. Soc.116. 4221-4226 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] 野田健二: "Catalytic Asymmetric Oxidation of Sulfides Using (salen)manganese(III) Complex as a Catalyst" Tetrahedron. 50. 9609-9618 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] 野依良治: "Stereoselective Organic Synthesis via Dynamic Kinetic Resolution" Bull. Chem. Soc. Jpn.68. 36-55 (1995)

    • Related Report
      1994 Annual Research Report
  • [Publications] 笠井宏明: "Catalytic Asymmetric Michael Reactions Promoted by a Lithium-Free Lanthanum-BINOL Complex" J. Am. Chem. Soc.116. 1571-1572 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] 畠中康夫: "Catalytic Asymmetric Hydrosilylation of Conjugated Dienes: Effective Control of Regio and Enantioselectivities" Tetrahedron Lett.35. 7981-7982 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] 林 民生: "Ferrocenes" VCH Verlagsgesellshaft, 1-540 (1995)

    • Related Report
      1994 Annual Research Report
  • [Publications] 林民生: "Catalytic Asymmetric Reduction of Allylic Esters with Formic Acid Catalyzed by Palladium-MOP Complexes" J.Am.Chem.Soc.116. 775-776 (1994)

    • Related Report
      1993 Annual Research Report
  • [Publications] 林民生: "A New Optically Active Monodentate Phosphine Ligand,(R)-(+)-3-Diphenyl-phosphino-3'-methoxy-4,4'-biphenanthryl(MOP-phen). Preparation and......" Synthesis. (印刷中). (1994)

    • Related Report
      1993 Annual Research Report
  • [Publications] 林民生: "Optically Active Ruthenocenylbisphosphines: New Efficient Chiral Phosphine Ligands for Catalytic Asymmetric Reactions" J.Am.Chem.Soc.(印刷中). (1994)

    • Related Report
      1993 Annual Research Report
  • [Publications] 魚住泰広: "Catalytic Asymmetric Construction of Morpholines and Piperazines by Palladium-Catalyzed Tandem Allylic Substitution Reactions" J.Org.Chem.58. 6826-6832 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] 小澤文幸: "Palladium-Catalyzed Asymmetric Arylation of 2,3-Dihydrofuran with Phenyl Triflate. A Novel Asymmetric Catalysis Involving a Kinetic Resolution Process" Organometallics. 12. 4188-4196 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] 松本米龍: "Preparation of Silafunctional Allylsilanes by Palladium-Catalyzed Silylation of Allylic Chlorides with 1,1-Dichloro-1-pheny1-2,2,2-trimethyldisilane" Organometallics. 12. 4051-4055 (1993)

    • Related Report
      1993 Annual Research Report

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Published: 1993-04-01   Modified: 2016-04-21  

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