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Development of Innovative Transformation by Using Synergistic Effect of Plural Metals

Research Project

Project/Area Number 19675002
Research Category

Grant-in-Aid for Young Scientists (S)

Allocation TypeSingle-year Grants
Research Field Synthetic chemistry
Research InstitutionThe University of Tokyo

Principal Investigator

NISHIBAYASHI Yoshiaki  The University of Tokyo, 工学(系)研究科(研究院), 准教授 (40282579)

Project Period (FY) 2007 – 2011
Project Status Completed (Fiscal Year 2011)
Budget Amount *help
¥79,950,000 (Direct Cost: ¥61,500,000、Indirect Cost: ¥18,450,000)
Fiscal Year 2011: ¥17,160,000 (Direct Cost: ¥13,200,000、Indirect Cost: ¥3,960,000)
Fiscal Year 2010: ¥17,160,000 (Direct Cost: ¥13,200,000、Indirect Cost: ¥3,960,000)
Fiscal Year 2009: ¥17,160,000 (Direct Cost: ¥13,200,000、Indirect Cost: ¥3,960,000)
Fiscal Year 2008: ¥16,250,000 (Direct Cost: ¥12,500,000、Indirect Cost: ¥3,750,000)
Fiscal Year 2007: ¥12,220,000 (Direct Cost: ¥9,400,000、Indirect Cost: ¥2,820,000)
Keywords触媒反応 / ルテニウム / 不斉合成 / 窒素固定 / モリブデン / アンモニア / 多核錯体 / 銅 / 相乗効果 / タングステン / 複核錯体
Research Abstract

多核遷移金属錯体内に存在する金属-金属間の相互作用を利用する相乗効果によって特異的な反応性を発現させ、従来の単核金属錯体を用いた時には達成できなかった革新的な新規分子変換反応を開発することを最終目標とする。金属間結合を持つ多核遷移金属錯体上での特異な反応性の発現に関しては多くの研究者がその未知なる可能性について指摘してきたが、実際にその特異な反応性を見出した例は非常に限られている。本研究で得られる研究成果は、従来の概念を打ち破り、多核遷移金属錯体上での特異な分子変換反応が可能であることを示す次世代化学の先駆けと成り得る。具体的な研究課題は次の2つとである。1つ目は「複数の金属の相乗効果を利用する窒素分子の触媒的な分子変換反応の開発」、2つ目は「多核錯体上での有機分子の触媒的な新規分子変換反応の開発」である。本年度はPNP型ピンサー配位子を有するモリブデン窒素錯体を用いて窒素ガスからの触媒的アンモニア生成反応の開発に成功した。本触媒反応は窒素固定酵素ニトロゲナーゼのモデル反応でもあり、次世代型窒素固定法開発へ繋がる極めて興味深い研究成果である。不斉プロパルギル位置換反応の開発研究の一環として、光学活性持ホスフィンを有する銅錯体を用いたエナンチオ選択的なプロパルギル位アミノ化反応を開発することに成功し、その詳細な反応機構を解明することにも成功した。さらに、硫黄架橋2核ルテニウム錯体と有機触媒存在下で協奏的なプロパルギル位アルキル化反応を開発することにも成功した。

Report

(3 results)
  • 2010 Annual Research Report
  • 2009 Self-evaluation Report ( PDF )
  • 2007 Annual Research Report
  • Research Products

    (15 results)

All 2011 2010 2009 2008 2007 Other

All Journal Article (11 results) (of which Peer Reviewed: 6 results) Presentation (2 results) Remarks (2 results)

  • [Journal Article] A Molybdenum Complex Bearing PNP-Type Pincer Ligands Leads to the Catalytic Reduction of Dinitrogen into Ammonia2011

    • Author(s)
      K.Arashiba, et. al.
    • Journal Title

      Nature Chemistry

      Volume: 3 Pages: 120-125

    • Related Report
      2010 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Copper-Catalyzed Enantioselective Propargylic Amination of Propargylic Esters with Amines : Copper-Allenylidene Complexes as Key Intermediates2010

    • Author(s)
      G.Hattori, et. al.
    • Journal Title

      J.Am. Chem. Soc.

      Volume: 132 Pages: 10592-10608

    • Related Report
      2010 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Cccperative Catalytic Reactions Using Organocatalysts and Transition Metal Catalysts : Enantioselective Propargylic Alkylation of Propargylic Alcohols with A2010

    • Author(s)
      M.Ikeda, et. al.
    • Journal Title

      Angew. Chem. Int. Ed.

      Volume: 49 Pages: 7289-7293

    • Related Report
      2010 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Enantioselective Ring-Opening Reactions of Racemic Ethynyl Epoxides via Copper-Allenylidene Intermediates : Efficient Approach to Chiral b-Amino Alcohols2009

    • Author(s)
      G. Hattori, A. Yoshida, Y. Miyake, Y. Nishibayashi
    • Journal Title

      J.Org.Chem. 74

      Pages: 7603-7607

    • Related Report
      2009 Self-evaluation Report
  • [Journal Article] Ruthenium-Catalyzed Enantioselective Carbon-Carbon Bond Forming Reaction via Allenylidene-Ene Process : Synthetic Approach to Chiral Heterocycles such as Chromane, Thiochromane, and 1,2,3,4-Tetrahydroquinoline Derivatives2008

    • Author(s)
      K. Fukamizu, Y. Miyake, Y. Nishibayashi
    • Journal Title

      J.Am.Chem.Soc. 130

      Pages: 10498-10499

    • Related Report
      2009 Self-evaluation Report
  • [Journal Article] Copper-Catalyzed Asymmetric Propargylic Substitution Reactions of Propargylic Acetates with Amines : A Novel Synthetic Approach to Chiral Propargylic Amines2008

    • Author(s)
      G. Hattori, H. Matsuzawa, Y. Miyake, Y. Nishibayashi
    • Journal Title

      Angew.Chem.Int.Ed. 47

      Pages: 3781-3783

    • Related Report
      2009 Self-evaluation Report
  • [Journal Article] Ruthenium-Catalyzed Vinylic Substitution Reactions with Nucleophiles via Butatrienylidene Intermediates2008

    • Author(s)
      Yamauchi, M. Yuki, Y. Tanabe, Y. Miyake, Y. Inada, S. Uemura, Y. Nishibayashi
    • Journal Title

      J.Am.Chem.Soc. 130

      Pages: 2908-2909

    • Related Report
      2009 Self-evaluation Report
  • [Journal Article] Ruthenium-Catalyzed Enantioselective Propargylation of Aromatic Compounds with Propargylic Alcohols2007

    • Author(s)
      H. Matsuzawa, Y. Miyake, Y. Nishibayashi
    • Journal Title

      Angew.Chem.,Int.Ed. 46

      Pages: 6488-6491

    • Related Report
      2009 Self-evaluation Report
  • [Journal Article] Ruthenium-Catalyzed Reactions of 1-Cyclopropyl-2-propyn-1-ols with Anilines and Water via Allenylidene Intermediates2007

    • Author(s)
      Y. Yamauchi, et. al.
    • Journal Title

      J. Am. Chem. Soc. 129

      Pages: 5175-5179

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Ruthenium-Catalyzed Enantioselective Propargylation of Aromatic Compounds with Propargylic Alcohols via Allenylidene Intermediates2007

    • Author(s)
      H. Matsuzawa, et. al.
    • Journal Title

      Angew. Chem. Int. Ed. 46

      Pages: 6488-6491

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Design and Preparation of a Chiral Ligand Based on a Pseudorotaxane Skeleton2007

    • Author(s)
      G. Hattori, et. al.
    • Journal Title

      J. Am. Chem. Soc. 129

      Pages: 12930-12931

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Presentation] 複数の金属を利用した革新的分子変換反応の開発を目指して2010

    • Author(s)
      西林仁昭
    • Organizer
      第38回オルガノメタリックセミナー
    • Place of Presentation
      大阪大学
    • Year and Date
      2010-11-22
    • Related Report
      2010 Annual Research Report
  • [Presentation] 複核錯体の特性を用いる触媒反応の開発2007

    • Author(s)
      西林 仁昭
    • Organizer
      平成19年度後期有機合成化学講習会
    • Place of Presentation
      東京
    • Year and Date
      2007-11-21
    • Related Report
      2007 Annual Research Report
  • [Remarks]

    • URL

      http://park.itc.u-tokyo.ac.jp/nishiba/

    • Related Report
      2010 Annual Research Report
  • [Remarks]

    • URL

      http://park.itc.u-tokyo.ac.jp/nishiba/

    • Related Report
      2007 Annual Research Report

URL: 

Published: 2007-04-01   Modified: 2016-04-21  

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