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Development of New Reactions with Organometallic Reagents Stable in

Research Project

Project/Area Number 14078215
Research Category

Grant-in-Aid for Scientific Research on Priority Areas

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

Principal Investigator

OSHIMA Koichiro  Kyoto University, Department of Material Chemistry, Professor, 工学研究科, 教授 (00111922)

Project Period (FY) 2002 – 2005
Project Status Completed (Fiscal Year 2006)
Budget Amount *help
¥98,000,000 (Direct Cost: ¥98,000,000)
Fiscal Year 2005: ¥14,000,000 (Direct Cost: ¥14,000,000)
Fiscal Year 2004: ¥14,000,000 (Direct Cost: ¥14,000,000)
Fiscal Year 2003: ¥59,500,000 (Direct Cost: ¥59,500,000)
Fiscal Year 2002: ¥10,500,000 (Direct Cost: ¥10,500,000)
KeywordsAqueous Media / Nickel / Trialkylborane / Alkvlation / コバルト / 環境調和型反応 / ラジカル / 環化反応 / カップリング反応 / ラジカル反応 / ビニル化 / アリル化 / 有機インジウム化合物 / 有機カリウム化合物 / 金属アート錯体 / グリニャール反応剤 / アリル化反応 / シンナミルエーテル / 不飽和アルデヒドアセタール / 塩化クロム / 環状化合物
Research Abstract

The alkylation of aldehydes with organometallic reagents is one of the most important reactions in organic chemistry. Conventional alkylborane reagents do not react with aldehydes. We disclosed that nickel-catalyzed alkylation of aldehydes with trialkylboranes proceeds smoothly in the presence of a catalytic amount of η^2-ally1-1,2,3,4,5-pentamethy1-1,3-cyclopentadiene or an excess of cesium carbonate to afford the corresponding secondary alcohols. Trialkylboranes prepared from borane-dimethyl sulfide and terminal olefins via hydroboration as well as commercially available trialkylboranes could be employed for the reaction. The reaction would proceed via 12-coordinated nickel complexes with aldehydes as key intermediates. Interestingly, water enabled alkylation of aldehydes with trialkylboranes under nickel catalysis without additives.

Report

(5 results)
  • 2006 Final Research Report Summary
  • 2005 Annual Research Report
  • 2004 Annual Research Report
  • 2003 Annual Research Report
  • 2002 Annual Research Report
  • Research Products

    (19 results)

All 2006 2005 2004 Other

All Journal Article (13 results) Publications (6 results)

  • [Journal Article] Nickel-Catalyzed Reactions of Silacyclobutanes with Aldehydes : Ring Opening and Ring Expansion Reaction2006

    • Author(s)
      Koji Hirano et al.
    • Journal Title

      Organic Letters 8

      Pages: 483-485

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Alkylation of Aldehydes with Trialkylboranes in Water2006

    • Author(s)
      Koji Hirano et al.
    • Journal Title

      Advanced Synthesis and Catalysis 348

      Pages: 1543-1546

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Nickel-Catalyzed Reactions of Silacyckr butanes with Aldehydes : Ring Opening and Ring Expansion Reaction2006

    • Author(s)
      Koji Hirano et al.
    • Journal Title

      Organic Letters 8

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Alkylation of Aldehydes with Trialkyl- boranes in Water2006

    • Author(s)
      Koji Hirano et al.
    • Journal Title

      Advanced Synthesis and Catalysis 348

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Cobalt- and rhodium-catalyzed cross-coupling reaction of allylic ethers and halides with organometallic reagents2006

    • Author(s)
      Hiroto Yasui, Keiya Mizutani, Hideki Yorimitsu, Koichiro Oshima
    • Journal Title

      Tetrahedron 62

      Pages: 1410-1415

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Cobalt-catalyzed cross-coupling reactions of alkyl halides with aryl Grignard reagents and their application to sequential radical cyclization/cross-coupling reactions2006

    • Author(s)
      Hirohisa Ohmiya, Katsuyu Wakabayashi, Hideki Yorimitsu, Koichiro Oshima
    • Journal Title

      Tetrahedron 62

      Pages: 2207-2213

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Cobalt(diamine)-catalyzed Cross-coupling Reaction of Alkyl Halides with Arylmagnesium Reagents : Stereoselective Constructions of Arylated Asymmetric Carbons and Application to Total Synthesis of AH132052006

    • Author(s)
      Hirohisa Ohmiya, Hideki Yorimitsu, Koichiro Oshima
    • Journal Title

      Journal of the American Chemical Society 128

      Pages: 1886-1889

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Nickel-Catalyzed Alkylation of Aldehydes with Trialkylboranes2005

    • Author(s)
      Koji Hirano et al.
    • Journal Title

      Organic Letters 7

      Pages: 4689-4691

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Cobalt-Catalyzed Syn-Hydrophosphination of Alkynes2005

    • Author(s)
      Hirohisa Ohmiya, Hideki Yorimitsu, Koichiro Oshima
    • Journal Title

      Angewandte Chemie, International Editions 44

      Pages: 2368-2370

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Regio- and Stereoselective Approach to 1,2-Di- and 1,1,2-Trisilylethenes by Cobalt-Mediated Reaction or Silyl-Substituted Dibromomethanes with Silylmethylmagnesium Reagents2005

    • Author(s)
      Hirohisa Ohmiya, Hideki Yorimitsu, Koichiro Oshima
    • Journal Title

      Angewandte Chemie, International Editions 44

      Pages: 3488-3490

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Recent advances in the use of tri(2-furyl)germane2005

    • Author(s)
      Hideaki Yorimitsu et al.
    • Journal Title

      Inorganic Chemistry Communications 8

      Pages: 131-143

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Radical Allylation, vinylation, alkynilation and Phenylation2005

    • Author(s)
      Kazuaki Takami
    • Journal Title

      Synthesis (in press)

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Radical Alkenylation of α-Halo Carbonyl Componds2004

    • Author(s)
      Kazuaki Takami et al.
    • Journal Title

      Organic Letters 6

      Pages: 4555-4558

    • Related Report
      2004 Annual Research Report
  • [Publications] Hidenori Kinoshita: "Pd(0)-Catalyzed Reaction of Alkynes with Trifurylgermane and CO Provinding Acylgermanes : Hydrometalcarbonylation of Alkynes"J. Am. Chem. Soc.. 124・16. 4220-4221 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Yousuke Ikeda: "Cobalt-Catalyzed Heck-Type Reaction of Alkyl Halides with Styrenes"J. Am. Chem. Soc.. 124・23. 6514-6515 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Kazuaki Takami: "Trans-Hydrometalation of Alkynes by a Combination of InCl_3 and DIBAL-H : One-Pot Access to Functionalized (Z)-Alkenes"Org. Lett.. 4・17. 2993-2995 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Satoshi Mikami: "Palladium-Catalyzed Coupling Reaction of Alkenylgalliums with Aryl Halides"Synlett. 7. 1137-1139 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Takashi Tsuji: "Cobalt-Catalyzed Coupling Reaction of Alkyl Halides with Allylic Grignard Reagents"Angew. Chem. Int. Ed.. 41・21. 4137-4139 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Takuma Fujioka: "Cobalt-Catalyzed Intramolecular Heck-Type Reaction of 6-Halo-1-hexene Derivatives"Org. Lett.. 4・13. 2257-2259 (2002)

    • Related Report
      2002 Annual Research Report

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Published: 2002-04-01   Modified: 2018-03-28  

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