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Development of Novel Synthetic Methods Based on Selective Oxidation of Organometallics

Research Project

Project/Area Number 08455417
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field 有機工業化学
Research InstitutionOsaka University

Principal Investigator

HIRAO Toshikazu  Osaka University, Faculty of Engineering, Professor, 工学部, 教授 (90116088)

Co-Investigator(Kenkyū-buntansha) MORIUCHI Toshiyuki  Osaka Univ., Faculty of Engineering, Assistant, 工学部, 助手 (60281119)
OGAWA Akiya  Osaka Univ., Faculty of Engineering, Associate Professor, 工学部, 助教授 (30183031)
Project Period (FY) 1996 – 1997
Project Status Completed (Fiscal Year 1997)
Budget Amount *help
¥7,700,000 (Direct Cost: ¥7,700,000)
Fiscal Year 1997: ¥1,400,000 (Direct Cost: ¥1,400,000)
Fiscal Year 1996: ¥6,300,000 (Direct Cost: ¥6,300,000)
Keywordsorganoaluminum / ate complex / oxidative coupling reaction / oxovanadium / redox / 酸化反応 / カップリング反応 / 有機ジルコニウム化合物
Research Abstract

One-electron oxidation or reduction of organometallics by one-electron redox with transition metals permits a novel reaction behavior based on the change of the electronic state on metals, which is considered to provide novel synthetic reactions. If transmetallation is taken place instead, the reactivities based on the characteristics of the introduced metals are expected to widen the scope of stnthetic methods via organometallic intermediates. Oxovanadium compounds with one-electron oxidation capability are employed for this purpose in this research project. The oxidative transformations of organometallics have been investigated to provide versatile methods for selective carbon-carbon bond formation.
1) Organoaluminum ate complexes obtained by treatment of alkenylaluminums with alkyllithiums underwent oxidative coupling with oxovanadium oxidant to afford the corresponding enynes selectively. This reaction was found to be applied to a variety of organoaluminum compounds.
2) The similar oxidative coupling reaction proceeded well starting from arylaluminums in stead of alkenyl ones.
3) The direct oxidation of aryldialkylaluminums with oxovanadium compounds led to the introduction of an alkyl group to give the alkyl-substituted arenes. The steric bulkiness and redox potentials of oxovanadium compounds reflected on the oxidative coupling. The one-pot transformations are possible without isolation of the intermediate complexes and considered to be of synthetically potetial. The redox interaction between organometallics and oxovanadium compounds is likely to permit these transformations. The coupling is recognized to be formal reductive elimination of main-group organometallics, which has been less accessible by conventional methods.

Report

(3 results)
  • 1997 Annual Research Report   Final Research Report Summary
  • 1996 Annual Research Report
  • Research Products

    (6 results)

All Other

All Publications (6 results)

  • [Publications] Toshikazu Hirao: "Vanadium in Modern Organic Synthesis" Chemical Reviews. 97-8. 2707-2724 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] 平尾 俊一: "有機化学基礎の基礎" 化学同人, 23 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] T.Hirao: "Vanadium in Modern Organic Synthesis" Chem.Rev.Vol.97, No.8. 2707-2725 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Toshikazu Hirao: "Vanadium in Modern Organic Synthesis" Chemical Reviews. 97-8. 2707-2724 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] Toshikazu Hirao: "Vanadium in Modern Organic Synthesis" Chemical Reviews. (印刷中).

    • Related Report
      1996 Annual Research Report
  • [Publications] Toshikazu Hirao: "Topics in Current Chemistry Selective Transformations of Small Ring Compounds in Redox Reactions" Springer-Verlag, 49 (1996)

    • Related Report
      1996 Annual Research Report

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Published: 1996-04-01   Modified: 2016-04-21  

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