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Enantioface-Differentiating Protonation with Chiral Charcogen Compounds on the Basis of Original Molecular Design

Research Project

Project/Area Number 07672261
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Chemical pharmacy
Research InstitutionTOYAMA MEDICAL AND PHARMACEUTICAL UNIVERSITY

Principal Investigator

TAKAHASHI Tamiko  Toyama Medical & Pharmaceutical University, Faculty of Pharmaceutical Sciences, Research Associate, 薬学部, 助手 (10115181)

Project Period (FY) 1995 – 1996
Project Status Completed (Fiscal Year 1996)
Budget Amount *help
¥1,400,000 (Direct Cost: ¥1,400,000)
Fiscal Year 1996: ¥600,000 (Direct Cost: ¥600,000)
Fiscal Year 1995: ¥800,000 (Direct Cost: ¥800,000)
Keywordschiral selenoxide / gamma-hydroxyselenoxide / asymmetric protonation / prochiral enolate / ZnBr / intramolecular hydrogen bonding / chelation effect
Research Abstract

1. We have developed a facile method for the preparation of arylselenoxides having electron-withdrawing or electron-donating group.
2. An optically pure gamma-hydroxyselenoxide was available for a chiral proton source (CPS).
3. Enantioselectivity of this reaction was improved by introduction of an electron-donating group to benzene ring of CPS.4-Methoxy group was the most effective.
4. Reaction of zinc bromide enolates of 2-benzyl-and 2-n-propylcyclohexanones with (S_<Se>) -selenoxide (Ar=p-MeOC_6H_4) gave (S) -2-benzylcyclohexanone and (R) -2-n-propyl-cyclohexan-one in 89% ee and 88%ee, respectively.
5. This asymmetric induction is probably due to intramolecular hydrogen bonding between hydroxy group and seleninyl-oxygen as well as chelation effects among hydroxy group, seleninyl-oxygen and metal enolate.

Report

(3 results)
  • 1996 Annual Research Report   Final Research Report Summary
  • 1995 Annual Research Report
  • Research Products

    (25 results)

All Other

All Publications (25 results)

  • [Publications] T. Takahashi et al.: "Nucleofilic Substitution Reaction of Optically Pure Chloroselenurane with Active Methylene Compounds. Formation of OIptically Pure Selenonium Ylides" Chemistry Letters. (5). 379-380 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Y. Nakajima-Yamakoshi et al.: "High Pressure Mediated Asymmetric Diels-Alder Reaction of Chiral Sulfinyl-acrylate Derivatives with Furan and 2-Methoxyfuran" Heterocycles. 42 (1). 129-133 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] T. Takahashi et al.: "The First Example of Enantioselective Protonation of Prochiral Enolates with Chiral γ-Hydroxyselenoxides" Chemistry Letters. (3). 207-208 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] N. Kurose et al.: "Asymmetric [2, 3] Sigmatropic Rearrangement of Chiral Allylic Selenimides" J. Org. Chem.61 (9). 2932-2933 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] T. Takahashi et al.: "First Synthesis and Structure of Optically Pure Te-Chiral-Alkoxytelluranes" Tetrahedron Asymmetry. 7 (10). 2797-2800 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] J. Ziang et al.: "Optically Pure Alkoxychlorosulfuranes. Synthesis and Transformation to Chiral Sulfoxides, N-p-Tosylsulfilimines, and Sulfonium Ylides" Heterocycles. 44 (1). 325-339 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] N. Kurose et al.: "Asymmetric [2, 3] Sigmatropic Rearrangement of Chiral Allylic Selenonium Ylides" J. Org. Chem.62. 000-000 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] J. Ziang et al.: "Synthesis of Cyclic Halooxatelluranes via Dehalogenation of α-Halo Carbonyl Compounds with Tellurides Containing Hydroxy Group on Side Chain" Heterocycles. 45. 000-000 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] T.Takahashi, N.Kurose, S.Kawanami, A.Nojiri, Y.Arai, T.Koizumi, M.Shiro :"Nucleophilic Substitution Reaction of Optically Pure Chloroselenurane with Active Methylene Compounds. Formation of Optically Pure Selenonium Ylides" Chem. Lett.(5). 379-380 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Y.Nakajima-Yamakoshi, W.-Y.Ge, J.Sugita, K.Okayama, T.Takahashi, and T.Koizumi :"High Pressure Mediated Asymmetric Diels-Alder Reaction of Chiral Sulfinylacrylate Derivatives with Furan and 2-Methoxyfuran" Heterocycles. 42 (1). 129-133 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] T.Takahashi, N.Nakao, and T.Koizumi :"The First Example of Enantioselective Protonation of Prochiral Enolates with Chiral gamma-Hydroxyselenoxides" Chem. Lett.(3). 207-208 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] N.Kurose, T.Takahashi, and T.Koizumi :"Asymmetric [2, 3] Sigmatropic Rearrangement of Chiral Allylic Selenimides" J.Org. Chem.61 (9). 2932-2933 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] T.Takahashi, J.Ziang, N.Kurose, S.Takahashi, and T.Koizumi :"First Synthesis and Structure of Optically Pure Te-Chiral-Alkoxytelluranes" Tetrahedron Asymmetry. 7 (10). 2797-2800 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] J.Ziang, T.Takahashi, and T.Koizumi :"Optically Pure Alkoxychlorosulfuranes. Synthesis and Transformation to Chiral Sulfoxides, N-p-Tosylsulfil-imines, and Sulfonium Ylides" Heterocycles. 44 (1). 325-339 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] N.Kurose, T.Takahashi, and T.Koizumi :"Asymmetric [2, 3] -Sigmatropic Rearrangement of Chiral Allylic Selenonium Ylides" J.Org. Chem.62 (in press.). (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] J.Ziang, S.Saito, T.Takahashi, and T.Koizumi :"Synthesis of Cyclic Halooxatelluranes via Dehalogenation of alpha-Halo Carbonyl Compounds with Tellurides Containing Hydroxy Group on Side Chain" Heterocycles. 45 (in press.). (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] T.Takahashi et al.: "Nucleofilic Substitution Reaction of Optically Pure Chloroselenurane with Active Methylene Compounds. Formation of OIptically Pure Selenonium Ylides" Chemistry Letters. (5). 379-380 (1995)

    • Related Report
      1996 Annual Research Report
  • [Publications] Y.Nakajima-Yamakoshi et al.: "High Pressure Mediated Asymmetric Diels-Alder Reaction of Chiral Sulfinyl-acrylate Derivatives with Furan and 2-Methoxyfuran" Heterocycles. 42(1). 129-133 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] T.Takahashi et al.: "The First Example of Enantioselective Protonation of Prochiral Enolates with Chiral γ-Hydroxyselenoxides" Chemistry Letters. (3). 207-208 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] N.Kurose et al.: "Asymmetric [2,3] Sigmatropic Rearrangement of Chiral Allylic Selenimides" J.Org.Chem.61(9). 2932-2933 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] T.Takahashi et al.: "First Synthesis and Structure of Optically Pure Te-Chiral-Alkoxytelluranes" Tetrahedron Asymmetry. 7(10). 2797-2800 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] J.Ziang et al.: "Optically Pure Alkoxychlorosulfuranes. Synthesis and Transformation to Chiral Sulfoxides, N-p-Tosylsulfilimines,and Sulfonium Ylides" Heterocycles. 44(1). 325-339 (1997)

    • Related Report
      1996 Annual Research Report
  • [Publications] N.Kurose et al.: "Asymmetric [2,3] Sigmatropic Rearrangement of Chiral Allylic Selenonium Ylides" J.Org.Chem.62. 000-000 (1997)

    • Related Report
      1996 Annual Research Report
  • [Publications] J.Ziang et al.: "Synthesis of Cyclic Halooxatelluranes via Dehalogenation of α-Halo Carbonyl Compounds with Tellurides Containing Hydroxy Group on Side Chain" Heterocycles. 45. 000-000 (1997)

    • Related Report
      1996 Annual Research Report
  • [Publications] T.Takahashi,N.Nakao,and T.Koizumi: "The First Example of Enantioselective Protonation of Prochiral Enolates with Chiral γ-Hydroxyselenoxides" Chemistry Letters. (1996)

    • Related Report
      1995 Annual Research Report

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Published: 1995-04-01   Modified: 2016-04-21  

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