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金属と微量の異種金属の相乗作用

Research Project

Project/Area Number 19027040
Research Category

Grant-in-Aid for Scientific Research on Priority Areas

Allocation TypeSingle-year Grants
Review Section Science and Engineering
Research InstitutionOkayama University

Principal Investigator

高井 和彦  Okayama University, 大学院・自然科学研究科, 教授 (00144329)

Project Period (FY) 2007
Project Status Completed (Fiscal Year 2007)
Budget Amount *help
¥2,700,000 (Direct Cost: ¥2,700,000)
Fiscal Year 2007: ¥2,700,000 (Direct Cost: ¥2,700,000)
Keywords相乗効果 / レニウム / 金 / ジエチニルメタン / 銅 / キノリン / インジウム / レトロClaisen反応
Research Abstract

金属触媒を2種類以上用いると、単独の触媒では行なえない変換反応が進行したり、効率的に多段階の反応が行なえる。新たな金属錯体触媒の組合せを検討し、同時に用いることで、その相乗効果により、官能基選択性や効率の高い新反応を開拓した。具体的には下記の3つの反応を見いだした。
(1)レニウムと金触媒を同時に用いるジエチニルメタンのワンポット合成:触媒量の塩化金(I)とレニウム錯体[ReBr(CO)_3(thf)]_2を同時に用いることで、アルデヒドと2当量のシリルアセチレンからジエチニルメタンを一挙に合成できることを見いだした。
(2)銅(I)、金(I)触媒によるN-アリールプロパルギルアミンからの2,4-二置換キノリン合成:触媒量のCuCiとAgOTf、あるいはAuClとAgOTfを用い、さらにアルジミンを1当量加え、N-アリールプロパルギルアミン7を加熱すると、2,4-二置換キノリンが高収率で得られることを見いだした。
(3)インジウム触媒によるレトロClaisen縮合反応:エノラートとエステルが反応して1,3-ジケトンが生じる反応はClaisen縮合反応として知られている。この逆反応が触媒量のインジウム錯体In(OTf)_3を用いると高収率で進行することを見いだした。この反応を利用すると、ケトンとエステルの両方をもつ化合物を容易に合成できる。

Report

(1 results)
  • 2007 Annual Research Report
  • Research Products

    (16 results)

All 2007 Other

All Journal Article (9 results) (of which Peer Reviewed: 9 results) Presentation (5 results) Book (1 results) Remarks (1 results)

  • [Journal Article] Rhenium and Gold-Catalyzed Coupling of Aromatic AIdehydes with Trimethyl(2-Phenylethynyl)silane; Synthesis of Diethynylmethanes2007

    • Author(s)
      Kuninobu, Y.; Ishii, E.; Takai, K.
    • Journal Title

      Angew. Chem. Int. Ed. 46

      Pages: 3296-3299

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Rhenium-Catalyzed Amidation of Heteroaromatic Compounds via C.H Bond Activation2007

    • Author(s)
      Kuninobu, Y.; Tokunaga, Y.; Takai, K.
    • Journal Title

      Chem. Lett. 36

      Pages: 872-873

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Rhenium-Catalyzed Synthesis of Naphthalene Derivatives via Insertion of Aldehydes into a C-H Bond.2007

    • Author(s)
      Kuninobu, Y.; Nishina, Y.; Takai, K.
    • Journal Title

      Tetrahedron 63

      Pages: 8463-8468

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Rearrangement of Indene Skeletons under Mild Conditions2007

    • Author(s)
      Kuninobu, Y.; Ueda, H.; Kawata, A.; Takai, K.
    • Journal Title

      J. Org. Chem. 7

      Pages: 6749-6752

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Manganese-Catalyzed Insertion of Aldehydes into a C-H Bond2007

    • Author(s)
      Kuninobu, Y.; Nishina, Y.; Takeuchi, T;. Takai, K.
    • Journal Title

      Angew. Chem. Int. Ed. 46

      Pages: 6518-6520

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Rhenium-Catalyzed [2+2] Cycloadditions of Norbornenes with Internal and Terminal Acetylenes2007

    • Author(s)
      Kuninobu, Y.; P.; Takai, K.
    • Journal Title

      Chem. Lett. 36

      Pages: 1162-116

    • NAID

      10019845985

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Indium-Catalyzed Retro-Claisen Condensation2007

    • Author(s)
      Kawata, A.; Takata, K.; Kuninobu, Y.; Takai, K.
    • Journal Title

      Tetrahedron 46

      Pages: 7793-7795

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Copper(I) and Gold(I)-Catalyzed Synthesis of 2,4-Disubstituted Quinoline Derivatives from N-Aryl Propargyl Amines2007

    • Author(s)
      Kuninobu, Y.; Inoue, Y.; Takai, K.
    • Journal Title

      Chem. Lett. 36

      Pages: 1422-1423

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Rhenium-Catalyzed Hydroamidation of Unactivated Terminal Alkynes:Synthesis of (E)-Enamides2007

    • Author(s)
      Yudha S. S.; Kuninobu, Y.; Takai, K.
    • Journal Title

      Org. Lett. 9

      Pages: 5609-56119

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Presentation] 有機合成反応の開発-ステンドグラスの楽しみ方2007

    • Author(s)
      高井和彦
    • Organizer
      第34回有機反応懇談会
    • Place of Presentation
      大阪
    • Year and Date
      2007-07-27
    • Related Report
      2007 Annual Research Report
  • [Presentation] レニウム触媒による炭素-水素活性化を基盤とする分子変換2007

    • Author(s)
      高井和彦, 國信洋一郎
    • Organizer
      特定領域研究「高度分子変換」第3回公開シンポジウム
    • Place of Presentation
      札幌
    • Related Report
      2007 Annual Research Report
  • [Presentation] Rhenium- and Aniline-Catalyzed One- Pot Annulation of Aromatic Ketones and α,β-Unsaturated Esters2007

    • Author(s)
      Takai, K.; Kuninobu, Y.; Nishina, Y.; Shouho, M.; Okaguchi, K.
    • Organizer
      14th IUPAC International Symposium on Organometallic Chemistry Directed Towards Organic Synthesis
    • Place of Presentation
      Nara
    • Related Report
      2007 Annual Research Report
  • [Presentation] Metal Activation by Addition of Catalytic Amounts of Different Metals - Synergistic Effects2007

    • Author(s)
      Takai, K.
    • Organizer
      The 1st International Symposium on Synergy of Elements
    • Place of Presentation
      Tokyo
    • Related Report
      2007 Annual Research Report
  • [Presentation] Rhenium- and Aniline- Catalyzed [3+2] Annulation of Aromatic Ketones and α,β-Unsaturated Esters2007

    • Author(s)
      Takai, K.; Kuninobu, Y.; Nishina, Y.; Shouho, M.
    • Organizer
      International Symposium on Catalysis and Fine Chemicals 2007
    • Place of Presentation
      Singapore
    • Related Report
      2007 Annual Research Report
  • [Book] Comprehensive Organometallic Chemistry III (VOl.11, Chap.11.02 Reductive Coupling Reactions Promoted by Low-valent Early Transition Metals and Lanthanoids)2007

    • Author(s)
      Takai, K.(分但執筆)(Crabtree, R. H.; Mingos, M. P.; Hiyama, T. Eds.)
    • Total Pages
      34
    • Publisher
      Elsevier; Amsterdam
    • Related Report
      2007 Annual Research Report
  • [Remarks]

    • URL

      http://achem.okayama-u.ac.jp/omc/paper.html

    • Related Report
      2007 Annual Research Report

URL: 

Published: 2007-04-01   Modified: 2018-03-28  

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