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電子移動触媒を利用した高効率高選択的不斉触媒反応の開発

Research Project

Project/Area Number 04J08398
Research Category

Grant-in-Aid for JSPS Fellows

Allocation TypeSingle-year Grants
Section国内
Research Field Functional materials chemistry
Research InstitutionOsaka University
Research Fellow 湯浅 順平  大阪大学, 大学院工学研究科, 特別研究員(PD)
Project Period (FY) 2004 – 2006
Project Status Completed (Fiscal Year 2006)
Budget Amount *help
¥2,800,000 (Direct Cost: ¥2,800,000)
Fiscal Year 2006: ¥900,000 (Direct Cost: ¥900,000)
Fiscal Year 2005: ¥900,000 (Direct Cost: ¥900,000)
Fiscal Year 2004: ¥1,000,000 (Direct Cost: ¥1,000,000)
Keywords電子移動 / キラル / 金属イオン / キノン系補酵素 / ヒドリド移動 / ルイス酸 / ラジカルアニオン / NADH / 不斉 / ダイマーラジカルアニオン / ESR / 集合化 / 電子アクセプター / キラルルイス酸触媒 / スカンジウムイオン
Research Abstract

補酵素類縁体であるp-および炉キノン類のラジカルアニオン種と金属イオンとの錯体をESRによって直接検出し、このラジカルアニオン-金属イオン錯体の結合様式を系統的に明らかにした。このようなラジカルアニオン-金属イオン錯体の結合様式とキノン類の電子移動反応との関係を調べ明確にした。また、この結合様式の違いを温度によって制御することで新規なサーモクロミズムシステムを構築した。さらにプロトン化されたアミノ酸と水素結合したセミキノンラジカルアニオン種をESRによって初めて直接検出することに成功し、キノン類の電子移動反応がセミキノンラジカルアニオン種とプロトン化されたアミノ酸と水素結合することで促進されることを見いだした。(Abgew.Chem.Int.Ed.,2007,46,in press)
一方、NADH類縁体からキノン類への水素移動及びヒドリド移動反応機構が一段階の移動機構(2電子過程)から電子-プロトンの逐次的な移動機構(1電子過程)へと切り替わる反応の境界領域を明らかにした。(J.Am.Chem.Soc.2006,128,4938-14948;J.Am.Chem.Soc.2006,128,14281-14292.)さらに金属イオンと架橋配位子の段階的な錯形成を利用して、特定の金属イオン濃度域でのみ発光する蛍光センサーのシステムを開発した。(J.Am.Chem.Soc.2006,128,15976)

Report

(3 results)
  • 2006 Annual Research Report
  • 2005 Annual Research Report
  • 2004 Annual Research Report

Research Products

(11 results)

All 2007 2006 2005 2004

All Journal Article (11 results)

  • [Journal Article] Direct ESR Detection of a Hydrogen-Bonded Complex between a Semiquinone Radical Anion and a Protonated Amino Acid and Electron Transfer Driven by the Hydrogen Bond2007

    • Author(s)
      Yuasa, J.et al.
    • Journal Title

      Angew.Chem.Int.Ed 46(in press)

    • Related Report
      2006 Annual Research Report
  • [Journal Article] A Mechanistic Dichotomy in Scandium Ion-Promoted Hydride Transfer of an NADH Analogue : Delicate Balance between One-Step Hydride-Transfer and Electron-Transfer Pathways2006

    • Author(s)
      Yuasa, J.et al.
    • Journal Title

      J.Am.Chem. oc. 128

      Pages: 14281-14281

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Mechanistic Borderline of One-Step Hydrogen Transfer vs Sequential Electron-Proton Transfer in Formal Hydrogen Transfer from NADH Analogs to the Triplet Excited States of Tetrazines and Ru(bpy)_3^<2+>2006

    • Author(s)
      Yuasa, J.et al.
    • Journal Title

      J.Am.Chem.Soc. 128

      Pages: 14938-14938

    • Related Report
      2006 Annual Research Report
  • [Journal Article] An OFF-OFF-ON Fluorescence Sensor for Metal Ions in Stepwise Complex Formation of 2,3,5,6-Tetrakis(2-pyridyl)pyrazine (TPPZ) with Metal Ions2006

    • Author(s)
      Yuasa, J.et al.
    • Journal Title

      J.Am.Chem.Soc. 128

      Pages: 15976-15976

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Binding Modes in Metal Ion Complexes of Quinones and Semiquinone Radical Anions : Electron-Transfer Reactivity2006

    • Author(s)
      Yuasa, J. et al.
    • Journal Title

      ChemPhysChem (in press)

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Remarkable Oxidizing Ability of Triplet Excited States of Tetrazines_Produced by Photosensitization with Ru(bpy)_3^<2+>2006

    • Author(s)
      Yuasa, J. et al.
    • Journal Title

      Chem.Commun (in press)

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Thermochromism of Metal Ion Complexes of Semiquinone Radical Anions. Control of Equilibria between Diamagnetic and Paramagnetic Species by Lewis Acids2005

    • Author(s)
      Yuasa, J. et al.
    • Journal Title

      J.Phys.Chem.A 109

      Pages: 9362-9362

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Mechanism of Scandium Ion-Catalyzed Diels-Alder Reaction of Anthracenes with Methyl Vinyl Ketone2005

    • Author(s)
      Yuasa, J. et al.
    • Journal Title

      J.Phys.Chem.A 109(in press)

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Thermochromism of Disproportionation Equilibrium of -Dimer Radical Anion Complexes Bridged by Scandium Ions2004

    • Author(s)
      Yuasa, J. et al.
    • Journal Title

      Org.Bimol.Chem. 2

      Pages: 642-642

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Scandium Ion-Catalyzed Photoinduced Electron Transfer from Electron Donors to Pyrene and Acridine Photocatalytic Oxygenation of Alkylbenzenes2004

    • Author(s)
      Yuasa, J. et al.
    • Journal Title

      J.Am.Chem.Soc. 126

      Pages: 7585-7585

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Drastic Changes in the Lifetime and Electron Transfer and Energy Transfer Reactivity of the Triplet Excited State of p-Benzoquinone by Complex Formation with Scandium Ion Salts2004

    • Author(s)
      Yuasa, J. et al.
    • Journal Title

      J.Phys.Chem.A 108

      Pages: 8333-8333

    • Related Report
      2004 Annual Research Report

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Published: 2004-03-31   Modified: 2016-04-21  

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