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Novel Carbon-Carbon Bond Formation Utilizing Selective C-H Bond Insertion by Carbenes.

Research Project

Project/Area Number 63470080
Research Category

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

Allocation TypeSingle-year Grants
Research Field Synthetic chemistry
Research InstitutionKyoto Institute of Technology

Principal Investigator

OKU Akira  Kyoto Institute of Technology, Department of Chemistry, Professor., 工芸学部, 教授 (50027885)

Co-Investigator(Kenkyū-buntansha) KAMADA Tohru  Kyoto Institute of Technology, Department of Chemistry, Assistant., 工芸学部, 助手 (30214513)
HARADA Toshiro  Kyoto Institute of Technology, Department of Chemistry, Associate Professor., 工芸学部, 助教授 (30135628)
Project Period (FY) 1988 – 1989
Project Status Completed (Fiscal Year 1989)
Budget Amount *help
¥5,100,000 (Direct Cost: ¥5,100,000)
Fiscal Year 1989: ¥700,000 (Direct Cost: ¥700,000)
Fiscal Year 1988: ¥4,400,000 (Direct Cost: ¥4,400,000)
Keywordscarbene / carbenoid / C-H insertion / organic synthesis / cyclopropanol / electron transfer / oxonium ylide / シクロプロパノ-ル / 電子移動反応 / オキソニウムイオン
Research Abstract

1988: (1) Optimized reaction conditions for regioselective C-H insertion or alkoxides by a variety of carbenes were examined. (2) In addition to alkoxides, other substrates which undergo selective insertion by carbenes were investigated. Enolate anion, nitrile carbanion, and alkyllithium were found to undergo selective - C-H insertion.
1989: (3) Promotion effect of t-BuOK on the reaction of bromolithiocarbenoids at low temperatures was found and their reactivity as carbene sources was investigated. (4) Reaction of cyclopropanol derivatives such as cyclopropanone hemiacetals and cyanohydrins with unencumbered carbenes yielded novel ring-opened cycloadduct propionates in high yields. (5) A novel-type of three-component joint reactions between cyclic etliercarbene - nucleophile was investigated to find that the formation of oxonium ylide intermediate is the key step of this reaction.

Report

(3 results)
  • 1989 Annual Research Report   Final Research Report Summary
  • 1988 Annual Research Report
  • Research Products

    (18 results)

All Other

All Publications (18 results)

  • [Publications] Akira Oku: "Stereochemical Aspects in the Insertion by Alkylidenemethylene Carbenoids into the -C-H Bond of Alkoxides." J.Org.Chem.53. 3086-3098 (1988)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] Akira Oku: "Promotion Effetc of t-BuOK on the Reaction of Bromolithio-catbenoids at Low temperatures." J.Chem.Soc.,Chem.Commun.1988. 1490-1491 (1988)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] Toshiro Harada: "Generation and Alkyaltion Reaction of 1-Bromoalkenylzincate." Tetrahedron Lett.29. 3821-3824 (1988)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] Toshiro Harada: "Generation and Alkyaltion of Lethium 1-Halocyclopropyfzincate." Tetrahedron Lett.30. 6035-6038 (1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] Akira Oku: "Novel-Ring-Opening AdditionReaction of Cyclopropanols With Carbene." J.Chem.Soc.,Chem.Commun.1990. (1990)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] Toshiro Harada: "Steroselective Synthesis of gem-Disubstituted Cyclopropanes from gem-Dibromocyclopropanes." Tetrahedron Lett.30. 6039-6040 (1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] A. Oku, T. Harada, K. Hattori, Y. Nozaki: "Stereochemical Aspects in the Insertion by Alkylidenemethylene Carbenoids into the -C-H Bond of Alkoxides." J. Org. Chem., 53, 3089-3098 (1988).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] A. Oku, T. Harada, Y. Homoto: "Promotion Effect of t-BuOK on the Reaction of Bromolithio-Carbenpoids at Low Temperature." J. Chem. Soc., Chem. Commun., 1988, 1490-1491 (1988).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] T. Harada, K. Hattori, T. Katsuhira, A. Oku: "Generation and Alkylation Reaction of 1-Bromoalkenylzincate." Tetrahedron Lett., 29, 3821-3824 (1988).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] T. Harada, T. Katsuhira, A. Oku: "Stereoselective Synthesis of gem-Disubstuted Cyclopropanes from gem-Dibromocyclopropanes." Tetrahedron Lett., 30, 6039-6040 (1989).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] T. Harada, D. Hara, K. Hattori, A. Oku: "Generation and Alkylation Reaction of 1-Bromoalkenylzincate." Tetrahedron Lett., 29, 3821-3824 (1988).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] T.Harada: "Generation and Alkylation of Lithium 1-Halocyclopropyl Zincate." Tetrahedron Lett.29. 6035-6038 (1989)

    • Related Report
      1989 Annual Research Report
  • [Publications] T.Harada: "Stereoselective Synthesis of gem-Disubstituted Cyclopropanes from gem-Dibromocyclopropanes." Tetrahedron Lett.29. 6039-6040 (1989)

    • Related Report
      1989 Annual Research Report
  • [Publications] A.Oku: "Novel Ring-Opening Addition Reaction of Cyclopropanols with Carbenes" J.Chem.Soc.,Chem.Commun.1990. (1990)

    • Related Report
      1989 Annual Research Report
  • [Publications] A.Oku: "Rhodium(II)-Catalyzed Intramolecular Carbenoid Reaction.Novel Ring-Cleaving Rearrangement of(Tetrahy drofurylacetyl)diazomethane" J.Am.Chem.Soc.

    • Related Report
      1989 Annual Research Report
  • [Publications] Akira Oku: J.Org.Chem.53. 3089-3098 (1988)

    • Related Report
      1988 Annual Research Report
  • [Publications] Akira Oku: J.Chem.Soc.,Chem.Commun.1988. 1490-1491 (1988)

    • Related Report
      1988 Annual Research Report
  • [Publications] Toshiro Harada: Tetrahedron Lett.29. 3821-3824 (1988)

    • Related Report
      1988 Annual Research Report

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Published: 1988-04-01   Modified: 2016-04-21  

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