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Development of Five-membered Ring Forming Reactions by Control of Electronic States of Biradical

Research Project

Project/Area Number 05403015
Research Category

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

Allocation TypeSingle-year Grants
Research Field 物質変換
Research InstitutionThe University of Tokyo (1995)
Tokyo Institute of Technology (1993-1994)

Principal Investigator

NAKAMURA Eiichi  The University of Tokyo, Gruduate School of Science, Professor, 大学院・理学系研究科, 教授 (00134809)

Project Period (FY) 1993 – 1995
Project Status Completed (Fiscal Year 1995)
Budget Amount *help
¥35,100,000 (Direct Cost: ¥35,100,000)
Fiscal Year 1995: ¥3,800,000 (Direct Cost: ¥3,800,000)
Fiscal Year 1994: ¥6,000,000 (Direct Cost: ¥6,000,000)
Fiscal Year 1993: ¥25,300,000 (Direct Cost: ¥25,300,000)
Keywordsbiradical / trimethylenemethane / vinglcarbene / pyrrolidine / five-membered rings / 付加環化反応 / フラーレン / ラジカル / 超音波 / 核酸切断 / 反応機構 / 抗ガン活性
Research Abstract

Focusing on the possibility of controlling the electronic structures of biradical species, the investigator carried out a research on the [3+2] cycloaddition reaction to form five-membered rings. As the result, electronic control of the trimethylenemethane (TMM) and vinyl radical (VC) species has been achieved to generate new dipolar three-carbon, four-electron reactive species, and the reactions of these species with two-electron acceptors have been developed to realize new synthesis of five-membered ring compounds. The major achievements are summarized as follows.
(1) Reactivity control of substituted TMM and VC species. By the use of the highly strained monocyclic rings, cyclopropene and methylenecyclopropane, the investigator performed kinetic studies on the TMM and VC formation reactions, and applied the results to the synthesis of cyclopentane and pyrollidine compounds. (2) Fullerene functionalization. TMM and VC have been found to react with fullerenes, and the results were applied for the studies various properties of water-soluble fullerenes including biological activities, monolayr formation, and synthesis of radioactive derivatives. (3) Ultrasound control of radical reactions. The ability of ultrasound irradiation for the control of radical reactions have been studied.

Report

(4 results)
  • 1995 Annual Research Report   Final Research Report Summary
  • 1994 Annual Research Report
  • 1993 Annual Research Report
  • Research Products

    (22 results)

All Other

All Publications (22 results)

  • [Publications] S. Yamago: "A Single Electron Transfer Pathway in the [3+2]Cycloaddition of Dipolar Trimethylenemethane with Olefins" J. Am. Chem. Soc.115. 5344-5345 (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] H. Tokuyama: "Photo-induced biochemical activity of fullerene carboxylic acid" J. Am. Chem. Soc.115. 7918-7919 (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] S. Yamago: "Synthesis and [2+2]Cycloaddition of Dimethyleneketene Acetals. Reaction with C60 and Facile Hydrolysis of the CC Bond Connected to C60" J. Am. Chem. Soc.116. 1123-1124 (1994)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] E. Nakamura: "Synthetic Chemistry of Cyclopropenone Acetals. Penitricin and Buckminsterfullerene" 有機合成化学協会誌. 52. 935-945 (1994)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] S. Yamago: "A Concise Synthetic Route to Cyclopentenes by [3+2]Cycloaddition of Dipolar Trimethylenemethane to Acetylenes" Angew. Chem.34. 2154-2156 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] S. Yamago: "In vivo Biological Behavior of Water-Miscible Fullerenes. 14C-Labeling,Absorption,Distribution,Excretion and Acute Toxicity" Chemistry & Biology. 2. 385-389 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] S.Yamago: "A Single Electron Transfer Pathway in the [3+2] Cycloaddition of Dipolar Trimethylenemethane with Olefins" J.Am.Chem.Soc.115. 5344-5345 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] H.Tokuyama: "Photo-induced biochemical activity of fullerene carboxylic acid" J.Am.Chem.Soc.115. 7918-7919 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] S.Yamago: "Synthesis and [2+2] Cycloaddition of Dimethyleneketene Acetals. Reaction with C60 and Facile Hydrolysis of the CC Bond Connected to C60" J.Am.Chem.Soc.116. 1123-1124 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] E.Nakamura: "Synthetic Chemistry of Cyclopropenone Acetals. Penitricin and Buckminsterfullerene" Journal of Organic Chemistry, Japan. 52. 935-945 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] S.Yamago: "A Concise Synthetic Route to Cyclopentenes by [3+2] Cycloaddition of Dipolar Trimethylenemethane to Acetylenes" Angew.Chem.34. 2154-2156 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] S.Yamago: "In vivo Biological Behavior of Water-Miscible Fullerences. 14C-Labeling, Absorption, Distribution, Excretion and Acute Toxicity" Chemistry & Biology. 2. 385-389 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] S.Yamago: "A Concise Synthetic Route to Cyclopentenes by [3+2] Cycloaddition of Dipolar Trimethylenemethane to Acetylenes" Angew.Chem.34. 2154-2156 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] T.Yamada: "cis-and tansDimethyl Spiro[(4′,4′-dimethyl-2′,6′-dioxacyclohexane)-1′3-(4-methylenebicyclo[3.3.0]octane)]-2,2-dicarboxylate" Acta Cryst.C51. 1137-1139 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] S.Yamago: "Synthesis and [2+2] Cycloaddition of Dimethyleneketene Acetals. Reaction with C60 and Facile Hydrolysis of the CC Bond Conected to C60" J.Am.Chem.Soc.116. 1123-1124 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] M.Matsumoto: "Langmuir-Blodgett Film of Amphiphilic C60 Carboxylic Acid." Lagmuir,. (印刷中). (1995)

    • Related Report
      1994 Annual Research Report
  • [Publications] E.Nakamura: "Sonochemical Initiation of Radical Chain Reactions. Hydrostannation and Hydroxystannation of C-C Multiple Bonds" J.Org.Chem.59. 8178-8179 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] S.Yamago: "Hydrostannation of cyclopropene. Strain-Driven Radical Addition Reaction" Chem.Lett.1889-1892 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] S.Yamago: "A Single Electron Transfer Pathway in the[3+2]Cycloaddition of Dipolar Trimethylenemethane with Olefins" J.Am.Chem.Soc.115. 5344-5345 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] H.Tokuyama: "Photo-induced biochemical activity of fullerene carboxylic acid" J.Am.Chem.Soc.115. 7918-7919 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] H.Tokuyama: "[1+2]and[3+2]Cycloaddition Reactions of Vinylcarbenes with C60" Tetrahedron Lett.34. 7429-7432 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] H.Tokuyama: "Regioselective Generation and Stereoselective[1+2]Cycloaddition of Vinylcarbenes" Synlett. 589-591 (1993)

    • Related Report
      1993 Annual Research Report

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Published: 1993-04-01   Modified: 2016-04-21  

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