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2007 Fiscal Year Final Research Report Summary

Design of Catalyst System for Enantioselective Borohydride Reduction with Environmental Benign

Research Project

Project/Area Number 18550099
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Synthetic chemistry
Research InstitutionKeio University

Principal Investigator

YAMADA Tohru  Keio University, Faculty of Science and Technology, Professor (40296752)

Project Period (FY) 2006 – 2007
KeywordsSynthetic Organic Chemistry / Catalysis / Chemical Industry / Cobalt
Research Abstract

The key reactive intermediate of borohydride reduction catalyzed by Schiff base-cobalt complexes is proposed to be the dichloromethyl-cobalt hydride with a sodium cation, based on experimental and theoretical studies. It was revealed that chloroform is not the solvent but the reactant that activates the cobalt catalyst. It was found that a catalytic amount of chloroform effectively activated the present catalytic system to convert various ketones into the corresponding reduced product with a high ee in the THF solvent. Furthermore, the theoretical simulation of various axial groups in cobalt complex catalysts predicted that the cobalt-carbene complexes could be employed as efficient catalysts. The newly designed complexes generated from cobalt complex and methyl diazoacetate made it possible to catalyze the enantioselective borohydride reduction in a halogen-free solvent.

  • Research Products

    (22 results)

All 2008 2007 2006

All Journal Article (16 results) (of which Peer Reviewed: 8 results) Presentation (2 results) Book (4 results)

  • [Journal Article] Catalytic Atropo-Enantioselective Reaction of Biaryl Lactones to Axially Chiral Biaryl Compounds2008

    • Author(s)
      T.Ashizawa, S.Tanaka, T.Yamada
    • Journal Title

      Organic Letters 10

    • Description
      「研究成果報告書概要(和文)」より
    • Peer Reviewed
  • [Journal Article] 光学活性コバルト錯体を触媒とする不斉シクロプロパン化反応と反応機構解析に基づく触媒設計2008

    • Author(s)
      池野 健人、佐藤 光央、岩倉 いずみ、小倉 あい、永田 卓司、山田 徹
    • Journal Title

      有機合成化学協会誌 66

      Pages: 110-123

    • Description
      「研究成果報告書概要(和文)」より
    • Peer Reviewed
  • [Journal Article] Enantioselective Borohydride Reduction Catalyzed by Cobalt Complexes:Discovery,Analysis,and Design for a Halogen-Free System2008

    • Author(s)
      T.Yamada
    • Journal Title

      Synthesis

      Pages: 1628-1640

    • Description
      「研究成果報告書概要(和文)」より
    • Peer Reviewed
  • [Journal Article] Catalytic Atropo-Enantioselective Reaction of Biaryl Lactones to Axially Chiral Biaryl Compounds2008

    • Author(s)
      T., Ashizawa, S., Tanaka, T., Yamada
    • Journal Title

      Organic Letters 10(in print)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Enantioselective Cycloprpanation Reaction Catalyzed by Optically Active Cobalt(II) Complexes and the Catalyst Design based on Theoretical Analysis2008

    • Author(s)
      T., Ikeno, M., Sato, I., Iwakura, A., Kokura, T., Nagata, T., Yamada
    • Journal Title

      Journal of Synthetic Organic Chemistry 66

      Pages: 110-123

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Enantioselective Borohydride Reduction Catalyzed by Cobalt Complexes : Discovery, Analysis, and Design for a Halogen-Free System2008

    • Author(s)
      T., Yamada
    • Journal Title

      Synthesis

      Pages: 1628-1640

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Newly Designed Catalysts for the Enantioselective Borohydride Reduction:Prediction from the Theoretical Analysis2007

    • Author(s)
      T.Ikeno, I.Iwakura, A.Shibahara, M.Hatanaka, A.Kokura, S.Tanaka, T.Nagata, T.Yamada
    • Journal Title

      Chemistry Letters 36

      Pages: 738-739

    • Description
      「研究成果報告書概要(和文)」より
    • Peer Reviewed
  • [Journal Article] Chloroform is Not Solvent but Activator for Cobalt Complex Catalyst for Enantioselective Borohydride Reduction2007

    • Author(s)
      A., Kokura, S., Tanaka, H., Teraoka, A., Shibahara, T., Ikeno, T., Nagata, T., Yamada
    • Journal Title

      Chemistry Letters 36

      Pages: 26-27

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Newly Designed Catalysts for the Enantioselective Borohydride Reduction : Prediction from the Theoretical Analysis2007

    • Author(s)
      T., Ikeno, I., Iwakura, A., Shibahara, M., Hatanaka, A., Kokura, S., Tanaka, T., Nagata, T., Yamada
    • Journal Title

      Chemistry Letters 36

      Pages: 738-739

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Catalytic Enantioselective Borohydride Reduction of ortho-Fluorinated B enzophenones2006

    • Author(s)
      A.Kokura, S.Tanaka, T.Ikeno, T.Yamada
    • Journal Title

      Organic Letters 8

      Pages: 3025-3027

    • Description
      「研究成果報告書概要(和文)」より
    • Peer Reviewed
  • [Journal Article] The Reactive Intermediate of Catalytic Borohydride Reduction by Schiff-base Cobalt Complexes2006

    • Author(s)
      I.Iwakura, M.Hatanaka, A.Kokura, H.Teraoka, T.Ikeno, T.Nagata, T.Yamada
    • Journal Title

      Chemistry-An Asian Journal 1

      Pages: 656-663

    • Description
      「研究成果報告書概要(和文)」より
    • Peer Reviewed
  • [Journal Article] Manganese and Cobalt 3-Oxobutylideneaminato Complexes:Design and Application for Enantioselective Reactions2006

    • Author(s)
      T.Yamada, T.Ikeno, Y.Ohtsuka, S.Kezuka, M.Sato, I.Iwakura
    • Journal Title

      Science and Technology of Advanced Materials 7

      Pages: 184-196

    • Description
      「研究成果報告書概要(和文)」より
    • Peer Reviewed
  • [Journal Article] Chloroform is Not Solvent but Activator for Cobalt Complex Catalyst for Enantioselective Borohydride Reduction2006

    • Author(s)
      A.Kokura, S.Tanaka, H.Teraoka, A.Shibahara, T.Ikeno, T.Nagata, T.Yamada
    • Journal Title

      Chemistry Letters 7

      Pages: 26-27

    • Description
      「研究成果報告書概要(和文)」より
    • Peer Reviewed
  • [Journal Article] Catalytic Enantioselective Borohydride Reduction of ortho-Fluorinated Benzophenones2006

    • Author(s)
      A., Kokura, S., Tanaka, T., Ikeno, T., Yamada
    • Journal Title

      Organic Letters 8

      Pages: 3025-3027

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] The Reactive Intermediate of Catalytic Borohydride Reduction by Schiff-base Cobalt Complexes2006

    • Author(s)
      I., Iwakura, M., Hatanaka, A., Kokura, H., Teraoka, T., Ikeno, T., Nagata, T., Yamada
    • Journal Title

      Chemistry -An Asian Journal 1

      Pages: 656-663

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Manganese and Cobalt 3-Oxobutylideneaminato Complexes : Design and Application for Enantioselective Reactions2006

    • Author(s)
      T., Yamada, T., Ikeno, Y., Ohtsuka, S., Kezuka, M., Sato, I., Iwakura
    • Journal Title

      Science and Technology of Advanced Materials 7(2)

      Pages: 184-196

    • Description
      「研究成果報告書概要(欧文)」より
  • [Presentation] 触媒設計の新しい可能性2008

    • Author(s)
      山田 徹
    • Organizer
      第55回有機合成化学協会関東支部シンポジウム
    • Place of Presentation
      東京理科大学野田キャンパス薬学校舎
    • Year and Date
      2008-05-09
    • Description
      「研究成果報告書概要(和文)」より
  • [Presentation] New Possibility of Catalyst Design2008

    • Author(s)
      Tohru, Yamada
    • Organizer
      The 55th Symposium of Kanto branch of the Society of Synthetic organic Chemistry, Japan
    • Place of Presentation
      Tokyo University of Science, Noda Campus
    • Year and Date
      2008-05-09
    • Description
      「研究成果報告書概要(欧文)」より
  • [Book] New Frontiers in Asymmetric Catalysis, Chapter 2"Ligand Design for Oxidation"2007

    • Author(s)
      T.Yamada
    • Total Pages
      26
    • Publisher
      Wiley-Interscience
    • Description
      「研究成果報告書概要(和文)」より
  • [Book] Design of Cobalt Complex Catalysts and Applications, Catalytic Enantioselective Reduction using SBH2007

    • Author(s)
      T.Yamada
    • Total Pages
      2
    • Publisher
      DMG world media
    • Description
      「研究成果報告書概要(和文)」より
  • [Book] Electronic Encyclopedia of Reagents for Organic Synthesis, (1S,2S)[N,N-Bis(2-acetyl-3-oxo-2-butylidene)-1,2-dimesitylethylenediaminato]cobait2007

    • Author(s)
      T.Yamada
    • Publisher
      Wiley(電子出版)
    • Description
      「研究成果報告書概要(和文)」より
  • [Book] 自然が選んだポルフィリン触媒の機能に学ぶ:ライフコンジュゲートケミストリー暮らしと未来を支える化学2006

    • Author(s)
      山田 徹
    • Total Pages
      25
    • Publisher
      三共出版
    • Description
      「研究成果報告書概要(和文)」より

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Published: 2010-02-04  

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