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Development and Application of Novel Ring-Expansion Reaction

Research Project

Project/Area Number 63550621
Research Category

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

Allocation TypeSingle-year Grants
Research Field 有機工業化学
Research InstitutionKYOTO UNIVERSITY

Principal Investigator

TAKEUCHI Ken'ichi  Kyoto Univ. Hydrocarbon Chemistry, Professor, 工学部, 教授 (50026358)

Co-Investigator(Kenkyū-buntansha) KINOSHITA Tomomi  Kyoto Univ. Hydrocarbon Chemistry, Lecturerer, 工学部, 助手 (10026289)
KOMATSU Koichi  Kyoto Univ. Hydrocarbon Chemistry, Associate Professor, 工学部, 助教授 (70026243)
Project Period (FY) 1988 – 1989
Project Status Completed (Fiscal Year 1989)
Budget Amount *help
¥1,800,000 (Direct Cost: ¥1,800,000)
Fiscal Year 1989: ¥500,000 (Direct Cost: ¥500,000)
Fiscal Year 1988: ¥1,300,000 (Direct Cost: ¥1,300,000)
KeywordsBridgehead aldehyde / Benzoyl triflate / Ring-expansion reaction / 1,2-Diol / 4-Homoadamantanones / Keto cation / Solvolysis reaction / Carbocation intermediate / 3位置換4ーホモアダマンタノン / 4ーオキソー2ーアダマンチル / 4ーメチレンー2ーアダマンチル / 新環拡大反応 / ホモアダマンタン誘導体 / ビシクロ化合物 / 橋頭炭素陽イオン / アリル共役 / ひずみエネルギー / スルーボンド相互作用 / カルボニル基
Research Abstract

1. Development of Nobel Ring-Expansion Reaction--Previously, we found a nobel ring-expansion of bridgehead aldehydes to 1,2-diol monobenzoates by use of benzoyl triflate. In this work, the method was applied to the bridgehead aldehydes of bicyclo [3.2.1] octyl, bicyclo[3.3.1] nonyl, and bicyclo[3.2.2] nonyl systems, and various new bicyclic 1,2-diols were successfully obtained. It was also demonstrated that the ring-expansion could be applied to the syntheses of bicyclic 1,2-diols labeled with ^2H or ^<13>C at the 2-position, 1-chlorobicyclo[2.2.2]octan-2-one, and various 3- alkyl(or aryl)-4-homoadamantanones.
2. Allylic Conjugation of 2-Methylene Bridgehead Carbocations--The logarithms of the rates of solvolysis of 2-methylene bridgehead compounds relative to the corresponding parent compounds were found to sigmoidally correlate with olefinic strain of the corresponding bridgehead olefins. The results, combined with our previous results on the rates of solvolysis of 2-oxo derivatives, showed that the delocalization of the positive charge of a 2-oxo carbocation to the carbonyl oxygen would be negligibly small. The methodology will be applied to the examination of the delocalization of positive charge to the imino or thiocarbonyl heteroatom.
3. Through-Bond Interaction in 3-Oxo Carbocations--The rates of solvolysis of 3-oxobicyclo[2.2.2]oct-l-yl derivatives were found 10^3 greater than expected from the inductive electron withdrawing effect of the carbonyl group. The rate and product studies demonstrated that the positive charge delocalizes to the carbonyl oxygen via through-bond interaction.

Report

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

    (12 results)

All Other

All Publications (12 results)

  • [Publications] 竹内賢一: "Syntheses of Bicyclic 1,2-Diols via the Ring-Expansion of Bridge-head Aldehydes of Bicyclo[3.2.1]octane and Bicyclononanes with Benzoyl triflate" Tetrahedron. 44. 5681-5694 (1988)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] 竹内賢一: "Evaluation of the π-Conjugative Effect of the 2-Methylene and the 2-Oxo Substituent on the Stability of Carbocations in the Solvolysis of Bicyclic Bridgehead Derivatives" Tetrahedron Lett.29. 873-876 (1988)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] 竹内賢一: "Solvolyses of 1-Adamantyl Triflate and Tresylate and 2-Adamantyl Tresylate:Y_<OTr> Scale and Relative Nucleofugalities of Various Leaving Groups Based on 1-Adamantyl Ethanolysis" J.Org.Chem.53. 2852-2855 (1988)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] 竹内賢一: "Unexpectedly Facile Solvolysis of 3-Oxobicyclo[2.2.2]Oct-1-yl Triflates:Through-Bond Interaction of the β-Carbonyl Lone Pair with the Cationic p Orbital" J.Org.Chem.54. 3772-3773 (1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] K. Takeuchi, K. Ikai, M. Yoshida, and A. Tsugeno: "Syntheses of Bicyclic 1,2-Diols via the Ring-Expansion of Bridgehead Aldehydes of Bicyclo[3.2.1]octane and Bicyclononanes with Benzoyl Triflate" Tetrahedron, 44, 5681-5694 (1988).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] K. Takeuchi, F. Akiyama, K. Ikai, T. Shibata, and M. Kato: "Evaluation of the pi-Conjugative Effect of the 2-Methylene and the 2-Oxo Substituent on the Stability of Carbocations in the Solvolysis of Bicyclic Bridgehead Derivatives" Tetrahedron Lett., 29, 873-876 (1988).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] K. Takeuchi, K. Ikai, T. Shibata, and A. Tsugeno: "Solvolyses of 1-Adamantyl Triflate and Tresylate and 2-Adamantyl Tresylate: Y_<OTr> Scale and Relative Nucleofugalities of Various Leaving Groups Based on 1-Adamantyl Ethanolysis" J. Org. Chem., 53, 2852-2855 (1988).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] K. Takeuchi and M. Yoshida: "Unexpectedly Facile Solvolysis of 3-Oxobicyclo[2.2.2]oct-1-yl Triflates: Through-Bond Interaction of the beta-Carbonyl Lone Pair with the Cationic p Orbital" J. Org. Chem., 54, 3772-3773 (1989).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] 竹内賢一: "Unexpectedly Facile Solvolysis of 3-Oxobicyclo[2.2.2]octーlーyl Triflates:ThroughーBond Interaction of the βーCarbonyl Lone Pair with the Cationic p Ocbital" J.Org.Chem.54. 3772-3773 (1989)

    • Related Report
      1989 Annual Research Report
  • [Publications] 竹内賢一: Tetrahedron. 44. 5681-5694 (1988)

    • Related Report
      1988 Annual Research Report
  • [Publications] 竹内賢一: J.Org.Chem.53. 2852-2855 (1988)

    • Related Report
      1988 Annual Research Report
  • [Publications] 竹内賢一: Tetrahedron Letters. 29. 873-876 (1988)

    • Related Report
      1988 Annual Research Report

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

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