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Creation of Proton Mediator Catalysts

Research Project

Project/Area Number 18550028
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Organic chemistry
Research InstitutionChiba University

Principal Investigator

YANAGISAWA Akira  Chiba University, Graduate School of Science, Professor (60183117)

Project Period (FY) 2006 – 2007
Project Status Completed (Fiscal Year 2007)
Budget Amount *help
¥4,120,000 (Direct Cost: ¥3,700,000、Indirect Cost: ¥420,000)
Fiscal Year 2007: ¥1,820,000 (Direct Cost: ¥1,400,000、Indirect Cost: ¥420,000)
Fiscal Year 2006: ¥2,300,000 (Direct Cost: ¥2,300,000)
KeywordsOrganic Reaction / Catalyst & Chemical Process / Asymmetric Protonation / Enolates / Chiral Catalysts
Research Abstract

In this research we attempted to develop chiral proton sources which make it possible to artificially control the position and reactivity of the proton and to prepare targeted organic compounds selectively with high optically purity in catalytic protonation reaction. During the term of this project, we especially examined novel chiral asymmetric catalysts possessing proton-mediator ability based on chiral Lewis acid catalysts. We have previously discovered that BINAP-AgF catalyst is an efficient chiral catalyst for catalytic asymmetric protonation of silyl enolates with MeOH. Thus, we investigated related chiral phosphine ligands and found that p-Tol-BINAP is able to provide higher enantioselectivity than that given by BINAP. In addition, high enantioselectivity was observed for silyl enolates derived from not only cyclic ketones but also acyclic ketones when a p-Tol-BINAP-AgF complex was used as a catalyst. Furthermore, use of ketene silyl acetals of biologically active α-aryl carboxylic acids such as ibuprofen and naproxen resulted in moderate asymmetric induction with up to 30% ee. In the meanwhile, as for exploration of organic proton-mediator catalysts based on oligopeptides, we tested a dipeptide consisting of aspartic acid and phenyl alanine as a chiral catalyst in the asymmetric protonation of lithium enolates and found that the dipeptide catalyst in combination of a bulky phenol as an achiral proton source gave the corresponding optically active ketones with up to 88% ee.

Report

(3 results)
  • 2007 Annual Research Report   Final Research Report Summary
  • 2006 Annual Research Report
  • Research Products

    (11 results)

All 2008 2006

All Journal Article (9 results) (of which Peer Reviewed: 4 results) Presentation (2 results)

  • [Journal Article] Recent Advances in Chiral Phosphine-Silver(I) Complex-Catalyzed Asymmetric Reactions2008

    • Author(s)
      A. Yanagisawa
    • Journal Title

      Chem. Commun.

      Pages: 1165-1172

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
    • Peer Reviewed
  • [Journal Article] Recent Advances in Chiral Phosphine-Silver (I) Complex-Catalyzed Asymmetric Reactions2008

    • Author(s)
      A. Yanagisawa, et. al.
    • Journal Title

      Chem. Commun

      Pages: 1165-1172

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Journal Article] Recent Advances in Chiral Phosphine-Silver(I)Complex-Catalyzed Asymmetric Reactions2008

    • Author(s)
      Akira Yanagisawa
    • Journal Title

      Chem.Commun

      Pages: 1165-1172

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Asymmetric Protonation of Silyl Enolates Catalyzed by Chiral Phosphine-Silver (I) Complex2006

    • Author(s)
      A. Yanagisawa
    • Journal Title

      Pure & Appl. Chem. 78

      Pages: 519-523

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
    • Peer Reviewed
  • [Journal Article] Catalytic Asymmetric Protonation of Lithium Enolates Using Amino Acid Derivatives as Chiral Proton Sources2006

    • Author(s)
      K. Mitsuhashi
    • Journal Title

      Org. Lett. 8

      Pages: 1721-1724

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
    • Peer Reviewed
  • [Journal Article] Asymmetric Protonation of Silyl Enolates Catalyzec by Chiral Phosphine-Silver (I) Complex2006

    • Author(s)
      A. Yanagisawa, et. al.
    • Journal Title

      Pure & Appl. Chem 78

      Pages: 519-523

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Journal Article] Catalytic Asymmetric Protonation of Lithium Enolates Using Amino Acid Derivatives as Chiral Proton Sources2006

    • Author(s)
      K. Mitsuhashi
    • Journal Title

      Org. Lett 8

      Pages: 1721-1724

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Journal Article] Asymmetric Protonation of Silyl Enolates Catalyzed by Chiral Phosphine-Silver(I) Complex2006

    • Author(s)
      Akira Yanagisawa
    • Journal Title

      Pure and Applied Chemistry Vol.78・No.2

      Pages: 519-523

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Catalytic Asymmetric Protonation of Lithium Enolates Using Amino Acid Derivatives as Chiral Proton Sources2006

    • Author(s)
      Kaori Mitsuhashi
    • Journal Title

      Organic Letters Vol.8・No.8

      Pages: 1721-1724

    • Related Report
      2006 Annual Research Report
  • [Presentation] 金属の特性を活かした高選択的反応の開発2008

    • Author(s)
      柳澤 章
    • Organizer
      RNシンポジウム2008
    • Place of Presentation
      名古屋大学
    • Year and Date
      2008-03-09
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Annual Research Report 2007 Final Research Report Summary
  • [Presentation] Development of Highly Selective Reactions Making Use of Characteristic of Metals2008

    • Author(s)
      A. Yanagisawa
    • Organizer
      RN Symposium 2008
    • Place of Presentation
      Nagoya
    • Year and Date
      2008-03-09
    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary

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Published: 2006-04-01   Modified: 2016-04-21  

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