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Highly Selective Carbon-carbon Bond Cleacage by Super-protic Directory Groups

Research Project

Project/Area Number 61470087
Research Category

Grant-in-Aid for General Scientific Research (B)

Allocation TypeSingle-year Grants
Research Field 有機工業化学
Research InstitutionToyohashi University of Technology

Principal Investigator

ITOH Kenji  Toyohashi University of Technology, 工学部, 教授 (60023149)

Co-Investigator(Kenkyū-buntansha) NISHIYAMA Hisao  Toyohashi University of Technology, 工学部, 助教授 (40135421)
Project Period (FY) 1986 – 1987
Project Status Completed (Fiscal Year 1987)
Budget Amount *help
¥5,300,000 (Direct Cost: ¥5,300,000)
Fiscal Year 1987: ¥300,000 (Direct Cost: ¥300,000)
Fiscal Year 1986: ¥5,000,000 (Direct Cost: ¥5,000,000)
KeywordsOrganosilicon Compound / Oxime / Beckmann Fragmentation / Organotin compounds / Ruthenium(IV) Complex / Activation of C-C bonds / イソキサゾリン / フラグメンテーション / 酸化開裂 / 高選択的開裂反応 / 複素環化合物
Research Abstract

The group 14 organometallic groups have been known to stabilize a carbocations locating at their <beta>. In this project, several extentions of this concept were investigated for seceloping highly selective cleavage processes of a -bond, such as carbon-carbon bonds unser moderate consitions Several<beta>-tri- methylsilylketoxime acetates were found to induce the highly regio-and strtro- specific Beckmann fragmentation to yield the corresponding alkeyl cyanides by an electrophilic activation with trimethylsilyl triflate. This methodology was much superior to the more common activation of a Si-C bond with flurides. This new fragmentation is particularly useful to the stereospecific fromation of olefins as exemplified by synthesis of several insect pheromones. Streroselective introduction of both metallyl function and the carbon moiety was achieved by the conjugate addition of alkenones in one-pot.
Alternatively, the organostannyl substituted ketoximes were found to cleave their <beta>-carbon-carbon bonds by oxidative activation with lead tetraacetate. This new process was also highly regio-and stereospecific to furnish alkenyl nitrile oxide intermediates, Which undergo intranolecular dipolar cycloadditions sponta- neously to give <DELTA>-isoxazolines. The super-protic natureof group 14 organo- metallyl groups was also applied to the selective decartboxylation of <beta>-metallyl- carboxylic acids and to the pyrazoline formation of tin-substituted hydrazines.
Modification of the cationic center to carbon to a transition-metal, an allylbromoruthenium(IV) moiety, resulted in an unprecedented silver fluoride activation of a carbon-silicon bond by way of a new methyl group migration from silicon to ruthenium atoms.

Report

(2 results)
  • 1987 Final Research Report Summary
  • 1986 Annual Research Report
  • Research Products

    (11 results)

All Other

All Publications (11 results)

  • [Publications] H. Nishiyama;M. Matsumoto;H. Arai;H. Sakaguchi;K. Itoh: Tetrahedron Letters. 27. 1599-1602 (1986)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1987 Final Research Report Summary
  • [Publications] H. Nishiyama;K. Sakuta;N. Osaka;H. Arai and K. Itoh: Tetrahedron. (1988)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1987 Final Research Report Summary
  • [Publications] K. Itoh and T. Fukahori: Journal of Organometallic Chemistry. (1988)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1987 Final Research Report Summary
  • [Publications] 岩村秀, 野依良治, 中井武, 北川勲編, 西山久雄, 伊藤健児: "「大学有機化学」(中)" 講談社サイエンティフィック,

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1987 Final Research Report Summary
  • [Publications] H. Nishiyama, Ma Matsumoto, H. Arai, H. Sakaguchi, and K. Iton: "Silicon- and Tin-directed Oxidative Decarboxylation: Regioselective Formation of Olefins from Beta-Silyl- and Beta-Stannyl Carboxylic Acids" Terahedron Letters. 27. 1599-1602 (1986)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1987 Final Research Report Summary
  • [Publications] H. Hishivama, K. Sakuta, N. Osaka, H. Arai, and K. Itoh: "Silicon-directed Beckmann Fragmentation" Tetrahedron. (1988)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1987 Final Research Report Summary
  • [Publications] K. Iton and T. Fukahori: "New Methyl Group Migration of a Trimethylsilymethylruthenum(iIv) Complex: An Unprecedented Reaction Mode of a Trimethylsilylmethyl Transition Metal Bond." Journal of Organometallic Chemistry. (1988)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1987 Final Research Report Summary
  • [Publications] H. Nishiyama and K. Iton: Kodansha Scientific Co. Ltd.Daigakuin Yuukikagaku (Advanced Organic Chemistry) Ed. by H. Iwamura, R. Noyori, T. Nakai, and I. Kitagawa,

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1987 Final Research Report Summary
  • [Publications] 西山久雄,金井勇樹,川嶋裕幸,新井宏幸,伊藤健児: Tetrahedron Letters. 27. 361-364 (1986)

    • Related Report
      1986 Annual Research Report
  • [Publications] 西山久雄,松本誠,新井宏幸,坂口久雄,伊藤健児: Tetrahedron Letters. 27. 1599-1602 (1986)

    • Related Report
      1986 Annual Research Report
  • [Publications] 西山久雄,坂口久雄,伊藤健児: Journal of the Chemical Society,Chemical Communication.

    • Related Report
      1986 Annual Research Report

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Published: 1987-03-31   Modified: 2016-04-21  

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