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Exploration of New Methodologies for Construction of Carbocycles their Synthetic Application

Research Project

Project/Area Number 62470019
Research Category

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

Allocation TypeSingle-year Grants
Research Field 有機化学一般
Research InstitutionTokyo Institute of Technology

Principal Investigator

KUWAJIMA Isao  Department of Chemitsry, A Faculty of Science, 理学部, 教授 (50016086)

Co-Investigator(Kenkyū-buntansha) URABE Hirokazu  Department of Chemistry, A Faculty of Science, 理学部, 助手 (10176745)
Project Period (FY) 1987 – 1988
Project Status Completed (Fiscal Year 1988)
Budget Amount *help
¥6,800,000 (Direct Cost: ¥6,800,000)
Fiscal Year 1988: ¥1,800,000 (Direct Cost: ¥1,800,000)
Fiscal Year 1987: ¥5,000,000 (Direct Cost: ¥5,000,000)
KeywordsCortisone / 3-(Silylmethyl)cyloalkenones / Taxane / One-Carbon Ring Enlarged Reactions / 2ー(シリルメチル)シクロアルカノン / 3-(シリルメチル)シクロアルケノン / 中員環環化法 / 2-(シリルメチル)シクロアルカノン / 共役付加
Research Abstract

We have investigated on new methodologies for construction of cyclic carbon frameworks either from (1) acyclic precursors and (2) cyclic ones.
(1) Generation of new nucleophilic species as metal homoenolates has been established, and several types of selective carbon-carbon bond forming reactions have been explored. These results can be applied for construction of steroidal carbon frameworks, and we succeeded to develop a useful methodology for a total synthesis of cortisone, involving a short and useful method for introduction of its side chain. Further, a useful methodology for construction of taxane ring system has also been developed. (2) Starting from 1-(TMS-methyl)cycloalkanecarbaldehydes and their derivatives, one-carbon ring expansion reactions involving cationic carbon skeleton rearrangement have been investigated. On generating carbocationic species stabilized by several hetero atoms, the ring carbon undergoes rearrangement selectively to afford the corresponding one-carbon ring enlarged products in high yields. Further, reactions of unsymmetrically substituted substrates have been studied, and migratory aptitude of a substituent has been proved as the following order: a sp^2-carbon > a more-substituted sp^3-carbon > a less-substituted sp@>D13@>D1-carbon.

Report

(3 results)
  • 1988 Annual Research Report   Final Research Report Summary
  • 1987 Annual Research Report
  • Research Products

    (23 results)

All Other

All Publications (23 results)

  • [Publications] E.Nakamura;S.Aoki;K.Sekiya;H.Oshino;I.Kuwajima: Journal of the American Chemical Society. 109. 8056-8066 (1987)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] I.Kuwajima: Pure & Appl.Chem.60. 115-122 (1988)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] S.Aoki;E.Nakamura;I.Kuwajima: Tetrahedron Letters. 29. 1541-1542 (1988)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] K.Tanino;T.Katoh;I.Kuwajima: Tetrahedron Letters. 29. 1815-1818 (1988)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] T.Katoh;K.Tanino;I.Kuwajima: Tetrahedron Letters. 29. 1819-1822 (1988)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] S.Aoki;T.Fujimura;E.Nakamura;I.Kuwajima: Journal of the American Chemical Society. 110. 3296-3298 (1988)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] E. Nakamura; S. Aoki; K. Sekiya; H. Oshino; I. Kuwajima: "Carbon-Carbon Bond Forming Reactions of Zinc Homoenolate of Esters. A Novel Three-Carbon Nucleophile with General Synthetic Utility" Journal of the American Chemical Society. 109. 8056-8066 (1987)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] I. Kuwajima: "1-Aikoxy-1-siloxycyclopropanes as Homoenolate Nuclephiles of Esters" Pure & Appl. Chem.60. 115-122 (1988)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] K. Tanino; T. Katoh; I. Kuwajima: "A Highly Selective One-Carbon Ring Enlargement Reaction Directed by Silicon" Tetrahedron Letters. 29. 1815-1818 (1988)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] T. Katoh; K. Tanino; I. Kuwajima: "A Highly Efficient Method for One-Carbon Ring Expansion. Preparation of 1-Alkoxy-2-Methylenecycloalkanes" Tetrahedron Letters. 29. 1819-1922 (1988)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] S. Aoki; T. Fujimura; E. Nakamura; I. Kuwajima: "Palladium-Catalyzed Arylation of Siloxycyclopropanes with Aryl Triflates. Carbon Chain Elongation via Catalytic Carbon-Carbon Bond Cleavage" Journal of the American Chemical Society. 110. 3296-3298 (1988)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] E.Nakamura;S.Aoki;K.Sekiya;H.Oshino;I.Kuwajima: Journal of the American Chemical Society. 109. 8056-8066 (1987)

    • Related Report
      1988 Annual Research Report
  • [Publications] I.Kuwajima: Pure & Appl. Chem.60. 115-122 (1988)

    • Related Report
      1988 Annual Research Report
  • [Publications] S.Aoki;E.Nakanura;I.Kuwajima: Tetrahedron Letters. 29. 1541-1542 (1988)

    • Related Report
      1988 Annual Research Report
  • [Publications] K.Tanino;T.Katoh;I.Kuwajima: Tetrahedron Letters. 29. 1815-1818 (1988)

    • Related Report
      1988 Annual Research Report
  • [Publications] T.Katoh;K.Tanino;I.Kuwajima: Tetrahedron Letters. 29. 1819-1822 (1988)

    • Related Report
      1988 Annual Research Report
  • [Publications] S.Aoki;T.Fujimura;E.Nakanura;I.Kuwajima: Journal of the American Chemical Society. 110. 3296-3298 (1988)

    • Related Report
      1988 Annual Research Report
  • [Publications] K.Tanino: Chemistry Letters. 385-388 (1987)

    • Related Report
      1987 Annual Research Report
  • [Publications] R.Matsuoka: Tetrahedron Letters. 28. 1299-1302 (1987)

    • Related Report
      1987 Annual Research Report
  • [Publications] K.Takanishi: Tetrahedron Letters. 28. 2281-2284 (1987)

    • Related Report
      1987 Annual Research Report
  • [Publications] H.Sakata: Tetrahedron Letters. 28. 5719-5722 (1987)

    • Related Report
      1987 Annual Research Report
  • [Publications] E.Nakamura: J.Am.Chem.Soc.109. 8056-8066 (1987)

    • Related Report
      1987 Annual Research Report
  • [Publications] K.Tanino: Tetrahedron Letters. (1988)

    • Related Report
      1987 Annual Research Report

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Published: 1987-04-01   Modified: 2016-04-21  

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