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Practical Synthesis of Chiral Building Blocks for Molecular Library of Organic Compounds

Research Project

Project/Area Number 13650919
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Synthetic chemistry
Research InstitutionKyoto Institute of Technology

Principal Investigator

HARADA Toshiro  Kyoto Institute of Technology, Faculty of Engineering and Design, Professor, 工芸学部, 教授 (30135628)

Project Period (FY) 2001 – 2002
Project Status Completed (Fiscal Year 2002)
Budget Amount *help
¥3,500,000 (Direct Cost: ¥3,500,000)
Fiscal Year 2002: ¥1,000,000 (Direct Cost: ¥1,000,000)
Fiscal Year 2001: ¥2,500,000 (Direct Cost: ¥2,500,000)
KeywordsAsymmetric Synthesis / Diol / Chiral Building BLock / Asymmetric Desymmetrization
Research Abstract

Enantiomerically enriched mono-protected derivatives of 2-substitued 1,3-propanediols are useful chiral building blocks which have been frequently employed in natural product synthesis. One of the moststraightforward methods for their preparation involves asymmetric desymmetrization of parent prochiral propanediols or their derivatives and enzyme-mediated transesterification or hydrolysis has been used for this purpose. A few reports have been appeared on nonenzymatic approach which could be of wide generality allowing to prepare a tailor-made chiral building blocks appropriate for the molecular library of organic compounds. Nonenzymatic desymmetrization of 2-substitutcd 1,3-propanediols leading to the enantiomerically enriched 3-benzyloxy-1-propanols was achieved by using from N-tosyl-(L)-naphthylalanine-derived oxazaborolidinone-mediated enantioselective ring-cleavage reaction of the dioxane acetal derivatives as a key reaction. The method was found to be highly effective for propanediols bearing a relatively bulky substituent at the 2 position. Further survey of reaction conditions to reduce the amount of the oxazaborolidinone revealed that the use of diethyl ether as an additive is effective. In the presence of the additive, highly selective ring-cleavage reaction was realized even when 0.5 equiv of oxamborolidinone was employed. In addition to this, the use of dimethylsilyl ketene S,O-acetal as a nucleophile is also found to be effective for the catalytic enantioselective ring-cleavage reaction.

Report

(3 results)
  • 2002 Annual Research Report   Final Research Report Summary
  • 2001 Annual Research Report
  • Research Products

    (15 results)

All Other

All Publications (15 results)

  • [Publications] Xiaowei Wang: "Practical Asymmetric Mukaiyama-Michael Reaction of Benzalacetone Derivatives Catalyzed by allo-Threonine-Derived Oxazaborolidinone"Chirality. 153. 28-30 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] 原田 俊郎: "Inter-and Intramolecular Differentiation of Enantiotopic Dioxane Acetals through Oxazaborolidinone-Mediated Enantioselective Ring-Cleavage Reaction : Kinetic Resolution of Racemic 1,3-Alkanediols and Asymmetric Desymmetrization of meso-1,3-Polyols"J. Org. Chem.. 67. 7080-7090 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] 原田 俊郎: "Asymmetric Desymmetrization of 2-Substituted 1,3-Propanediols by Using Oxaza-borolidinone-Mediated Enantioselective Ring-Cleavage of Prochiral Acetal Derivatives"Synlett. 972-974 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] 原田 俊郎: "Enantioselective Ring-Cleavage of Dioxane Acetals Mediated by a Chiral Lewis Acid : Application to Asymmetric Desymmetrization of meso-1,3-Diols"Org. Lett.. 3. 3309-3312 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] 原田 俊郎: "Asymmetric Mukaiyama-Michael Addition of Acyclic Enones Catalyzed by allo-Threonine Derived B-Aryloxazaborolidinones"Org. Lett.. 3. 2101-2103 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Xiaowei Wang: "Practical Asymmetric Mukaiyama-Michael Reaction of Benzalacetone Derivatives Catalyzed by allo-Threonine-Derived Oxazaborolidinone."Chirality. 153. 28-30 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Toshiro Harada: "Inter- and Intramolecular Differentiation of Enantiotopic Dioxane Acetals through Oxazaborolidinone-Mediated Enantioselective Ring-Cleavage Reaction: Kinetic Resolution of Racemic 1,3-Alkanediols and Asymmetric Desynimetrization of meso-1,3-Polyols."J. Org. Chem.. 67. 7080-7090 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Toshiro Harada: "Asynmretric Desymmetrization of 2-Substituted 1,3-Propanediols by Using Oxaza-borolidinone-Mediated Enantioselective Ring-Cleavage of Prochiral Acetal Derivatives."Synlett. 972-974 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Toshiro Harada: "Enantioselective Ring-Cleavage of Dioxane Acetals Mediated by a Chiral Lewis Acid: Application to Asymmetric Desymmetrization of meso- 1,3-Diols"Org. Lett.. 3. 3309-3312 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Toshiro Harada: "Asymmetric Mukaiyama-Michael Addition of Acyclic Enones Catalyzed by allo-Threonine Derived B-Aryloxazaborolidinones."Org. Lett.. 3. 2101-2103 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Xiaowei Wang: "Practical Asymmetric Mukaiyama-Michael Reaction of Benzalacetone Derivatives Catalyzed by allo-Threonine-Derived Oxazaborolidinone"Chirality. 153. 28-30 (2003)

    • Related Report
      2002 Annual Research Report
  • [Publications] 原田 俊郎: "Inter-and Intramolecular Differentiation of Enantiotopic Dioxane Acetals through Oxazaborolidinone-Mediated Enantioselective Ring-Cleavage Reaction : Kinetic Resolution of Racemic 1,3-Alkanediols and Asymmetric Desymmetrization of meso-1,3-Polyols"J.Org.Chem.. 67. 7080-7090 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] 原田 俊郎: "Asymmetric Desymmetrization of 2-Substituted 1,3-Propanediols by Using Oxaza-borolidinone-Mediated Enantioselective Ring-Cleavage of Prochiral Acetal Derivatives"Synlett. 972-974 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] 原田 俊郎: "Enantioselective Ring-Cleavage of Dioxane Acetals Mediated by a Chiral Lewis Acid : Application to Asymmetric Desymmetrization of meso-1, 3-Diols"Org.Lett.. 3. 3309-3312 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] 原田 俊郎: "Asymmetric Mukaiyama-Michael Addition of Acyclic Enones Catalyzed by allo-Threonine Derived B-Aryloxazaborolidinones"Org.Lett.. 3. 2101-2103 (2001)

    • Related Report
      2001 Annual Research Report

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Published: 2001-04-01   Modified: 2016-04-21  

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