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Reaction Control of Dynamic Complexes

Research Project

Project/Area Number 14078218
Research Category

Grant-in-Aid for Scientific Research on Priority Areas

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

Principal Investigator

KUROSAWA Hideo  Osaka University, Graduate School of Engineering, Professor, 大学院工学研究科, 教授 (40029343)

Project Period (FY) 2002 – 2005
Project Status Completed (Fiscal Year 2006)
Budget Amount *help
¥24,400,000 (Direct Cost: ¥24,400,000)
Fiscal Year 2005: ¥6,200,000 (Direct Cost: ¥6,200,000)
Fiscal Year 2004: ¥6,200,000 (Direct Cost: ¥6,200,000)
Fiscal Year 2003: ¥6,000,000 (Direct Cost: ¥6,000,000)
Fiscal Year 2002: ¥6,000,000 (Direct Cost: ¥6,000,000)
KeywordsTransition metal complex / Coordination flexibility / Dinuclear complex / 二核錯体 / 酸化的環化 / π-アリル錯体 / 有機金属錯体 / チオラート錯体 / アセチレン
Research Abstract

Coordination bonds of organotransition metal complexes are characterized by the flexibility of metal-carbon, metal-hetero atom, and metal-metal bonds. The flexibility is represented by facile bond formation and cleavage, as well as change of molecular parameters such as electron population, bond length and bond angle, in both static and dynamic molecular frameworks caused by a small physical and chemical stimuli applied to the complexes. This project aims at development of new synthetic methodology and functional materials through a systematic investigation of the structure-reactivity relation in organotransition metal complexes.
Llsomerization of allyl alcohol catalyzed by dinuclear ruthenium complexes
Dinuclear ruthenium complexes containing benzene ligand tethered by oxygen functional group were found to catalyze isomerization of allyl alcohols to the corresponding aldehydes and ketones. Key features of this catalysis are proposed to rely on facile coordination and dissociation of oxygen atoms of both substrates and the side arm of the benzene ligand. Specifically, the isomerization might have proceeded via coordination of allyloxo ligand, followed by β-H elimination and H shift to the terminal carbon of α, β-enone intermediate.
2.Coupling of η^2-ketone and η^2-alkene on nickel promoted by Me_3Al
Cyclization of carbonyl group and alkene group on nickel forming an oxanickelacycle has been postulated to be a key step in some nickel catalyzed coupling reactions. In this study a well-characterized η^2-carbonyl-η^2-alkene complex of nickel(0) was isolated and its structure determined. Treatment of this complex with Me_3Al promoted oxidative cyclization of carbonyl-alkene groups to give 5-membered oxanickelacycle with Ni coordinated by electron-deficient methyl bridge with AL

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

    (16 results)

All 2006 2005 2004 Other

All Journal Article (12 results) Publications (4 results)

  • [Journal Article] formation ofNickeladihydropyran by Oxidative Addition of Cyclopropyl Ketone. Key Intermediate in Nickel-catalyzed Cycloaddition.2006

    • Author(s)
      黒澤英雄, 他2名
    • Journal Title

      J. Am. Chem. Soc. 128

      Pages: 5350-5351

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Reversible Carbon-carbon Bond Formation between 1,3-Dienes and Aldehydes or etones on Nickel(0).2006

    • Author(s)
      黒澤英雄, 他3名
    • Journal Title

      J. Am. Chem. Soc. 128

      Pages: 7077-7086

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Formation of Nickeladihydropyran by Oxidative Addition of Cyclopropyl Ketone. Key Intermediate in Nickel-catalyzed Cycloaddition.2006

    • Author(s)
      S.Ogoshi, M.Nagata, H.Kurosawa
    • Journal Title

      J. Am. Chem. Soc 128

      Pages: 5350-5351

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Reversible Carbon-carbon Bond Formation between 1, 3-Dienes and Aldehydes or Ketones on Nickel(0).2006

    • Author(s)
      S.Ogoshi, K.Tonomori, M.Oka, H.Kurosawa
    • Journal Title

      J. Am. Chem. Soc 128

      Pages: 7077-7086

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] conversion of Allylic Alcohols to Carbonyl Compounds Catalyzed by Alkoxy-bridged Dinuclear Areneruthenium Complexes.2005

    • Author(s)
      黒澤英雄, 他4名
    • Journal Title

      Organometallics 24

      Pages: 4729-4733

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] AlMe_3 Promoted Oxidative Cyclization of η^2-Alkene and η^2-ketone on Nickel (0). Observation ofIntermediate in Methyl Transfer Process.2005

    • Author(s)
      黒澤英雄, 他3名
    • Journal Title

      J. Am. Chem. Soc. 127

      Pages: 12810-12811

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Conversion of Allylic Alcohols to Carbonyl Compounds Catalyzed by Alkoxy-bridged Dinuclear Areneruthenium Complexes.2005

    • Author(s)
      Y.Takai, R.Kitaura, E.Nakatani, T.Onishi, H.Kurosawa
    • Journal Title

      Organometallics 24

      Pages: 4729-4733

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] AlMe3 Promoted Oxidative Cyclization of μ2-Alkene and μ2-Ketone on Nickel (0). Observation of Intermediate in Methyl Transfer Process.2005

    • Author(s)
      S.Ogoshi, M.Ueta, T.Aral, H.Kurosawa
    • Journal Title

      J. Am. Chem. Soc. 127

      Pages: 12810-12811

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Conversion of Allylic Alcohols to Carbonyl Compounds Catalyzed by Alkoxy-bridged Dinuclear Areneruthenium Complexes2005

    • Author(s)
      Y.Takai, H.Kurosawa 他3名
    • Journal Title

      Organemetallics 24

      Pages: 4729-4733

    • Related Report
      2005 Annual Research Report
  • [Journal Article] AlMe_3-Promoted Oxidative Cyclization of η^2-Alkene and η^2-Ketone on Nickel(O). Observation of Intermediate in Methyl Transfer Process2005

    • Author(s)
      S.Ogoshi, H.Kurosawa 他2名
    • Journal Title

      J.Am.Chem.Soc. 127

      Pages: 12810-12811

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Direct Observation of Oxidative Cyclization of η^2-Alkene and η^2-Aldehyde on Ni(O) Center. Significant Acceleration by Addition of Me3SiOTf2004

    • Author(s)
      S.Ogoshi, M.Oka, H.Kurosawa
    • Journal Title

      J.Am.Chem.Soc. 126

      Pages: 11802-11803

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Dimerisation of Terminal Alkynes Catalysed by Nickel Complex Having Bulky phosphine Ligand2004

    • Author(s)
      S.Ogoshi, M.Ueta, M.Kurosawa
    • Journal Title

      Chem.Commun.

      Pages: 2732-2733

    • Related Report
      2004 Annual Research Report
  • [Publications] Sensuke Ogoshi, Masaki Morita, Hideo Kurosawa: "Synthesis, Structure and Reactivity of η^3-1-Hydroxyallyl Complex : Protonation of α,β-Unsaturated Carbonyl Compound Bound to Palladium(O) and Platinum (O)"J.Am.Chem.Soc.. 125. 9020-9021 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Masaki Morita, Katsuharu Inoue, Sensuke Ogoshi, Hideo Kurosawa: "Reaction of Palladium and Platinum Complexes Bearing α,β-Unsaturated Carbonyl Compounds with Carbon Electrophiles : Control over Site of Electrophilic Attack, Oxygen or Metal"Organometallics. 22. 5468-5472 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] T.Murahashi, T.Okuno, T.Nagai, H.Kurosawa: "Generation of Oligoene Species Capped by 2 Pd(II) Moieties from a Dinuclear Palladium(II) Complex and Alkyne"Organometallics. 21. 3679-3682 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] H.Kuniyasu, H.Kurosawa: "Transition-Metal-Catalyzed Carbon-Heteroatom Three-Component Cross-Coupling Reactions: A New Concept for Carbothiolation of Alkynes"Chem.Eur.J.. 8. 2661-2665 (2002)

    • Related Report
      2002 Annual Research Report

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

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