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Synthesis of optically active diols using electroreductive cuupling of ketone and double bond

Research Project

Project/Area Number 11650901
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Synthetic chemistry
Research InstitutionKinki University

Principal Investigator

KASHIMURA Shigenori  Department of Metallurgy, Kinki University Associatet Professor, 理工学部, 助教授 (50152632)

Co-Investigator(Kenkyū-buntansha) ISHIFUNE Manabu  Department of Applied Chemistry, Kinki University, Assistant Professor, 理工学部, 助手 (40268462)
Project Period (FY) 1999 – 2000
Project Status Completed (Fiscal Year 2000)
Budget Amount *help
¥2,700,000 (Direct Cost: ¥2,700,000)
Fiscal Year 2000: ¥1,100,000 (Direct Cost: ¥1,100,000)
Fiscal Year 1999: ¥1,600,000 (Direct Cost: ¥1,600,000)
KeywordsElectroreduction / Si atom / diol / Coupling / Regioselectivity / Bond formation / アルコール / カップリング反応
Research Abstract

It has been found in this study that, in the electroreductive intermolecular coupling of ketones with silyl substituted olefins, the existence of silyl group was found to play a important role for the regioselectivity and stereoselectivity of the reaction. This reaction is highly useful for the preparation of diols, formation of Si-Si bonds, and Si- carbon bonds. The elimination of Si atom in the coupling products was found to lead to the formation of the corresponding alcohols. This electroreductive method was also found to be useful for the reductive coupling of Si- and Ge-containing organic compounds. For examples, the electroreductive coupling of hydrosilanes led to the formation of new Si-Si and Si-C bonds with ordered sequences. The electroreduction of dichlorogerman gave poly- and oligo-germans, and poly silane-germans in good yields. By utilizing this method, the synthesis of optically active poly- and oligo-silanes has also been attained in this study.

Report

(3 results)
  • 2000 Annual Research Report   Final Research Report Summary
  • 1999 Annual Research Report
  • Research Products

    (18 results)

All Other

All Publications (18 results)

  • [Publications] 柏村成史: "Electroreductive Intramolecular Cyclization of Olefinic Esters and Its Application to the Synthesis of Muscone"Acta Chem, Scand.. 53. 949-951 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] 柏村成史: "Electroreductive Synthesis of Polysilanes, Polygermanes, and Related Polymers with Magnesium Electrodes"J.Org.Chem.,. 64(18). 6615-6621 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] 柏村成史: "Surface Oxidation and Activation of Carbon Fiber Using Radical NO3・Generated by Anodic Oxidation of NO3-"Electrochemistry,. 67(12). 1117-1119 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] 柏村成史: "Electroreductive Polymerization of Oligosilanes and Polysilanes with Ordered Sequences"J.Orgmet.Chem.,. 611. 26-31 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] 柏村成史: "New Paired Electrolysis System of Aliphatic Esters on Magnesium Cathode and Tetrahydrofuran on platinum anode"Acta.Chem.Scand.. (in press). (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] 柏村成史: "Preparation of Novel Modified Electrode by Anodic Oxidation of Carbon Fiber with Radical NO3・and Its Application to the Selective Reduction of Acetophenone"Acta.Chem.Scand.. (in press). (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Shigenori Kashimura, Yoshihiro Murai, Manabu Ishifune, Haruhisa Masuda, Masatoshi Shimomura, Hiroaki Murase, and Tatsuya Shono: "Electroreductive Intramolecular Cyclization of Olefinic Esters and Its Application to the Synthesis of Muscone."Acta Chem, Scand.. 53. 949-951 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Shigenori Kashimura, Manabu Ishifune, Natsuki Yamashita, Hang-Bom Bu, Masakatsu Takebayashi, Satsuki Kitajima, Daisuke Yoshiwara, Yasuki Kataoka, Ryoichi Nishida, Shin-ichi Kawasaki, Hiroaki Murase and Tatsuya Shono: "Electroreductive Synthesis of Polysilanes, Polygermanes, and Related Polymers with Magnesium Electrodes."J.Org.Chem.. 64(18). 6615-6621 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Shigenori Kashimura, Hiroya Kakegawa, Manabu Ishifune, Yoshihiro Murai, Yoshihiro Tamai, and Tatsuya Shono: "Surface Oxidation and Activation of Carbon Fiber Using Radical NO3・Generated by Anodic Oxidation of NO3-"Electrochemistry. 67(12). 1117-1119 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Manabu Ishifune, Shigenori Kashimura, a Yasumichi Kogai, Yasuyoshi Fukuhara, Tomo Kato, Hang-Bom Bu, Natsuki Yamashita, Yoshihiro Murai, Hiroaki Murase, and Ryoichi Nishida: "Electroreductive Polymerization of Oligosilanes and Polysilanes with Ordered Sequences"J.Orgmet.Chem.. 611. 26-31 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Manabu Ishifune, Hajime Yamashita, Masaharu Matsuda, Natsuki Yamashita, Shigenori Kashimura, Haruhisa Masuda, Hiroaki Murase: "New Paired Electrolysis System of Aliphatic Esters on Magnesium Cathode and Tetrahydrofuran on platinum anode."Acta.Chem.Scand.. (in press). (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Shigenori Kashimura, Yoshihiro Murai, Yoshihiro Tamai, and Ryuich Hirose, Manabu Ishifune, Hirokazu Iwase, Hajime Yamashita, and Natsuki Yamashita, Hiroya Kakegawa: "Preparation of Novel Modified Electrode by Anodic Oxidation of Carbon Fiber with Radical NO3・and Its Application to the Selective Reduction of Acetophenone"Acta.Chem.Scand.. (in press). (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] 柏村成史: "Electroreductive synthesis of oligosilanesand PolySilanes with ordered sequences"J.Orgmet.Chem. G11. 26-31 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] 柏村成史: "Preparation of Novel Modified electrade by Anodicoxidation of Carbon fiber with Radical NO_3^-"Electrochem.Acta. (印刷中). (2001)

    • Related Report
      2000 Annual Research Report
  • [Publications] 柏村成史: "Electroreduction of Aliphatic Esters using Paired Electrolysis System"Electrochem.Acta. (印刷中). (2001)

    • Related Report
      2000 Annual Research Report
  • [Publications] 柏村成史: "Electroreductive Intramolecular Cyclization of Olefinic Ester and its Application to the Synthesis of Muscone"Acta Chemica Scandinavica. 53卷. 949-951 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] 柏村成史: "Electroreductive Synthesis of Polysilanes,Polygermanes,and Related Polymers with Magnessium Electrodes"The Journal of Organic Chemistry. 64卷18号. 6615-66212 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] 柏村成史: "Surface Oxidation and Activation of Carbon Fiber Using NO_3 Generated by Anodic Oxidation of NO_3"Electrochemistry. 67卷12号. 1117-1119 (1999)

    • Related Report
      1999 Annual Research Report

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Published: 1999-04-01   Modified: 2016-04-21  

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