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Development of optically active transition metal complexes with molecular chirality

Research Project

Project/Area Number 06807162
Research Category

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

Allocation TypeSingle-year Grants
Research Field Chemical pharmacy
Research InstitutionTokyo University

Principal Investigator

SASAI Hiroaki  University of Tokyo Graduate School of Pharmaceutical Sciences, Lecturer, 大学院・薬学系研究科, 講師 (90205831)

Project Period (FY) 1994 – 1995
Project Status Completed (Fiscal Year 1995)
Budget Amount *help
¥2,100,000 (Direct Cost: ¥2,100,000)
Fiscal Year 1995: ¥900,000 (Direct Cost: ¥900,000)
Fiscal Year 1994: ¥1,200,000 (Direct Cost: ¥1,200,000)
Keywordsgallium / Rare Earth / Asymmetric Catalyst / Heterobimetallic / molecular chirality / Multifubctional Catalyst / アルミニウム / 光学活性錯体 / ガドリニウム / 光学活性遷移金属錯体 / ビフェノール錯体
Research Abstract

Asymmetric organometallic complexes are usually prepared from optically active compounds as ligands.However, some asymmetric complexes are reported to be exist without containing optically active ligands.Hitherto known stable these complexes with molecular chirality are prepared by optical resolution of racemic complexes and show no catalyst activity.In this study, we investigated asymmetric catalysts with molecular chirality.
So far, we have reported several multifunctional catalysts which contain (R) -or (S) -1,1'-bi-2-naphthol (BINOL) as a ligand.That is, the heterobimetallic lanthanoid catalysts promote asymmetric nitroaldol reactions, asymmetric Michael additions, asymmetric hydrophosphonylation of imines and/or aldehydes, etc.However when these type of lanthanoid complexes were prepared from achiral biphenol as a ligand, no asymmetric induction was observed due to the rapid ligand exchange.therefore we made examination of developing another type of complex with catalyst activity.After a number of attempts, we succeeded in obtaining asymmetric complexes which contain aluminum, and/or gallium by use of BINOL as a ligand.We also developed alkali metal free rare earth-BINOL complexes. These complexes were found to be effective in either asymmetric tandem Michael-aldol reactions, asymmetric ring opening of symmetric epoxides, or asymmetric epoxidation of enones.
Preparation of a rare earth complex from biphenol instead of BINOL in the presence of small amount of optically active diamines afforded a new complex with molecular chirality.Although the catalyst efficiency is unsatisfactory at present, we believe this type of complex would open up a new field in asymmetric synthesis.

Report

(3 results)
  • 1995 Annual Research Report   Final Research Report Summary
  • 1994 Annual Research Report
  • Research Products

    (7 results)

All Other

All Publications (7 results)

  • [Publications] Takayoshi Arai: "A New Multifunctional Heterobimetallic Asymmetric Catalyst for Michael Additions and Tandem Michael-Aldol Reactions" Angew.Chem.Int.Ed.Engl.35. 104-106 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Takayoshi Arai: "Self-Assembly of Heterobimetallic Complexes and Reactive Nucleophiles : A General Strategy for the Activation of Asymmetric Reactions Promoted by Heterobimetallic Catalysts" Chem.Eur.J.2. 1368-1372 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Masahiro Bougauchi: "Catalytic Asymmetric Epoxidation of α,β-Unsaturated Ketones Promoted by Lanthanoid Complexes" J.Am.Chem.Soc.119. 2329-2330 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Takayoshi Arai: "A New Multifunctional Heterobimetallic Asymmetric Catalyst for Michael Additions and Tandem Michael-Aldol Reactions" Angew.Chem.Int.Ed.Engl.35. 104-106 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Takayoshi Arai: "Self-Assembly of Heterobimetallic Complexes and Reactive Nucleophiles : A General Strategy for the Activation of Asymmetric Reactions Promoted by Heterobimetallic Catalysts" Chem.Eur.J.2. 1368-1372 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Masahiro Bougauchi: "Catalytic Asymmetric Epoxidation of alpha, beta-Unsaturated Ketones Promoted by Lanthanoid Complexes" J.Am.Chem.Soc.119. 2329-2330 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Takayoshi Arai: "A New Multifunctional Heterobimetallic Asymmetric Catalyst for Michael Additions and Tandem Michael-Aldol Reactions" Angew.Chem.Int.Ed.Engl.,. 35(in Press). (1996)

    • Related Report
      1995 Annual Research Report

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Published: 1994-04-01   Modified: 2016-04-21  

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