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Development of Asymmetric Selenoxide and Telluroxide Elimination.

Research Project

Project/Area Number 04453086
Research Category

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

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

Principal Investigator

UEMURA Sakae  Kyoto University, Graduate School of Engineering, Professor, 工学部, 教授 (70027069)

Co-Investigator(Kenkyū-buntansha) SUGITA Toshio  Kyoto University, Graduate School of Engineering, Professor, 工学部, 教授 (50027025)
杉田 利夫  京都大学, 工学部, 教授 (20025878)
Project Period (FY) 1992 – 1993
Project Status Completed (Fiscal Year 1993)
Budget Amount *help
¥7,200,000 (Direct Cost: ¥7,200,000)
Fiscal Year 1993: ¥1,700,000 (Direct Cost: ¥1,700,000)
Fiscal Year 1992: ¥5,500,000 (Direct Cost: ¥5,500,000)
Keywordsasymmetric synthesis / selenoxide elimination / telluroxide elimination / Chiral compound / [2,3]sigmatropic rearrangement / binaphthol / Sharpless oxidant / Davis oxidant
Research Abstract

We succeeded in asymmetric selenoxide elimination leading to chiral allenic sulfones and chiral alkyl and aryl cyclohexylidenemethyl ketones by oxidation of the corresponding selenides with chiral oxidants such as Sharpless oxidant and Davis oxidant. In the former case the maximum enatioselectivity was 42%ee, while in the latter case it reached to 83%ee. The nature of alkyl or aryl group of RSe or ArSe moiety had a remarkable effect on the ee value. On the other hand, we have not yet succeeded in asymmetric telluroxide elimination. In connection to these asymmetric reactions we were also successful in catalytic asymmetric oxidation of sulfides to sulfoxides with t-BuOOH using binaphthol as a chiral auxiliary and kinetic resolution of sulfoxides catalyzed by chiral titanium-binaphtholcomplex. Furthermore, we found that the Sharpless oxidation of some aryl cinnamyl selenides afforded a chiral 1-pheny1-2-propen-1-ol via asymmetric[2,3]sigmatropic rearrangement in a moderate to high selectivity(up to 92%ee).

Report

(3 results)
  • 1993 Annual Research Report   Final Research Report Summary
  • 1992 Annual Research Report
  • Research Products

    (22 results)

All Other

All Publications (22 results)

  • [Publications] Naoki Komatsu: "Asymmetric[2,3]Sigmatropic Rearrangement via Chiral Selenoxide with Sharpless Oxidants" Tetrahedron Lett.34. 2339-2342 (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Naoki Komatsu: "Asymmetric Selenoxide Elimination Leading to Chiral Allenic Sulfones" J.Org.Chem.58. 3697-3702 (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Naoki Komatsu: "Asymmetric Selenoxide Elimination Leading to Chiral Alkyl and Aryl Cyclohexylidenemethyl Ketones" J.Am.Chem.Soc.115. 5847-5848 (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Yoshiaki Nishibayashi: "Telluroxide Elimination by Oxidation of Alkyl Aryl Tellurides:Remarkable Effect of Added Triethylamine" J.Chem.Soc.,Perkin I. 1133-1138 (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Naoki Komatsu: "Catalytic Asymmetric Oxidation of Sulfides to Sulfoxides with tert-Butyl Hydroperoxide Using Binaphthol as a Chiral Auxiliary" J.Org.Chem.58. 4529-4533 (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Naoki Komatsu: "Kinetic Resolution of Sulfoxides Catalyzed by Chiral Titanium-Binaphthol Complex" J.Org.Chem.58. 7624-7626 (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Naoki Komatsu: "Advances in Detailed Reaction Mechanisms,Vol.4" Ed.by J.M.Coxon;JAI press,England,UK (in press), (1994)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] N.Komatsu et al.: "Asymmetric Selenoxide Elimination Leading to Chiral Allenic Sulfones" J.Org.Chem.58. 3697-3702 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] N.Komatsu et al.: "Asymmetric Selenoxide Elimination Leading to Chiral Alkyl and aryl Cyclohexylidenemethy1 Ketones" J.Am.Chem.Soc.115. 5847-5848 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] N.Komatsu et al.: "Asymmetric [2,3]Sigmatropic Rearrangement via Chiral Selenoxide with Sharpless Oxidants" Tetrahedron Lett.34. 2339-2342 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] N.Komatsu et al.: "Catalytic Asymmetric Oxidation of Sulfides to Sulfoxides with tert-Butyl Hydroperoxide Using Binaphthol as a Chiral Auxiliary" J.Org.Chem.58. 4529-4533 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] N.Komatsu et al.: "Kinetic Resolution of Sulfoxides Catalyzed by Chiral Titanium-Binaphthol Complex" J.Org.Chem.58. 7624-7626 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Y.Nishibayashi et al.: "Telluroxide Elimination by Oxidation of Alkyl aryl Tellurides" J.Chem.Soc., Perkin. I. 1133-1138 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] N.Komatsu et al.: "Synthetic and Mechanistic Aspects of Asymmetric Reactions of Organoselenium Compounds" Advances in Detailed Reaction Mechanisms, Vol.4, Ed.by J.M.Coxon ; JAI press, England, UK. (in press).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Naoki Komatsu: "Asymmetric Selenoxide Elimination Leading to Chiral Allenic" J.Org.Chem.58. 3697-3702 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] Naoki Komatsu: "Asymmetric Selenoxide Elimination Leading to Chirla Alkyl and Aryl Cyclohexylidenemethyl Ketones" J.Am.Chem.Soc.115. 5847-5848 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] Naoki Komatsu: "Catalytic Asymmetric Oxidation of Sulfides to Sulfoxides with tert-Butyl Hydroperoxide Using Binaphthol as a Chiral Auxiliary" J.Org.Chem.58. 4529-4533 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] Naoki Komatsu: "Kinetic Resolution of Sulfoxides Catalyzed by Chiral Titanium-Binaphthol Complex" J.Org.Chem.58. 7624-7626 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] Naoki Komatsu: "Advances in Detailed Reaction Mechanisms" Ed.by J.M.Coxon;JAI press,England,UK(in press), (1994)

    • Related Report
      1993 Annual Research Report
  • [Publications] Naoki Komatsu: "Catalytic Asymmetric Oxidation of Sulfides to Sulfoxides Using R-(+)-Binaphthol" Tetrahedron Letters. 33. 5391-5394 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] Naoki Komatsu: "Asymmetric [2,3]Sigmatropic Rearrangement via Chiral Selenoxide with Sharpless Oxidants" Tetrahedron Letters. 34. (1993)

    • Related Report
      1992 Annual Research Report
  • [Publications] Yoshiaki Nishibayashi: "Telluroxide Elimination by Oxidation of Alkyl Aryl Tellurides: A Remarkable Effect of Triethylamine Added" J.Chem.Soc.,Perkin 1. (1993)

    • Related Report
      1992 Annual Research Report

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Published: 1992-04-01   Modified: 2016-04-21  

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