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Practical Synthesis of Chiral Building Blocks by Highly Efficient Catalytic Asymmetric Acylation

Research Project

Project/Area Number 12554021
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section展開研究
Research Field Organic chemistry
Research InstitutionIBARAKI UNIVERSITY

Principal Investigator

ORIYAMA Takeshi  IBARAKI Univ., Fac. of Sci., Professor, 理学部, 助教授 (90185687)

Co-Investigator(Kenkyū-buntansha) YAMASAKI Noritsugu  DAICEL Chemical Industries, ltd., Research Associate, 筑波研究所・精密合成グループ, 主任研究員
Project Period (FY) 2000 – 2001
Project Status Completed (Fiscal Year 2001)
Budget Amount *help
¥9,600,000 (Direct Cost: ¥9,600,000)
Fiscal Year 2001: ¥1,300,000 (Direct Cost: ¥1,300,000)
Fiscal Year 2000: ¥8,300,000 (Direct Cost: ¥8,300,000)
Keywordschiral building block / practical synthesis / chiral 1,2-diamine / benzoyl chloride / triethylamine / kinetic resolution / asymmetrization / catalytic asymmetric acylation / キラル1,2-ジアミン / トリェケルアミン
Research Abstract

Recently, much attention has been focused on the non-enzymatic asymmetric acylation of racemic alcohols and meso-diols. We have already demonstrated asymmetric acylation of racemic secondary alcohols and meso-l,2-diols by the reaction with achiral benzoyl halide in the presence of a catalytic amount of chiral 1 , 2-diamine derived from (S)-proline. Some papers, which are based on the catalytic asymmetric acylation of alcohols with achiral acylating agents , have emerged successively in recent years. However, neither methodology has been developed to such a level as to find widespread use in organic synthesis.
We established that a chiral 1,2-diamine derived from (S)-proline could function as a highly efficient catalyst for the catalytic asymmetrization of meso- l , 2-diols. Catalytic asymmetric acylation of cw-2-cyclopentene- l ,4-diol has been successfully performed by the reaction with benzoyl chloride in the presence of 0. 5 mol% of chiral diamine combined with a stoichiometric amount of triethylamine to give the corresponding monobenzoate with excellent enantioselectivity. Thus obtained 4-benzoyloxy-2-cyclopenten-l-ol was readily converted to (R)-4-benzoyloxy-2-cyclopenten-1-one, a chiral building block for various prostaglandins, by the treatment of pyridinium dichromate (PDC). Catalytic asymmetric acylation of meso-1, 3-diols has been also successfully performed in the presence of only 0.5 mol% of chiral 1,2-diamine, combined with 1.5 equivalents of triethylamine. Catalytic kinetic resolution of racemic primary alcohols has been also performed with substituted benzoyl chloride in the presence of only 0.3 mol% of chiral 1,2-diamine derived from (S)-proline. This highly efficient asymmetric acylation of alcohols afforded various useful chiral building blocks.

Report

(3 results)
  • 2001 Annual Research Report   Final Research Report Summary
  • 2000 Annual Research Report
  • Research Products

    (23 results)

All Other

All Publications (23 results)

  • [Publications] T.Sano, K.Imai, K.Ohashi, T.Oriyama: "Catalytic Asymmetric Acylation of Racemic Secondary Alcohols with Beyrogl Chlonide in the Presence of a Chiral Diamine"Chem.Lett.. 265-266 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] T.Sano, K.Ohashi, T.Oriyama: "Remarkably Fast Acylation of Alcohols with Bengoyl Chloride Promoted by TMEDA"Synthesis. 1141-1144 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] 佐野智文, 折山剛: "キラルな1,2-ジアミンを用いるアルコール類の触媒的不斉アシル化の開発"有機合成化学協会誌. 57巻. 598-607 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] T.Sano, H.Miyata, T.Oriyama: "Highly Efficient Kinetic Resolution of B-Halohydrius Catalyzed by a Chiral 1,2-Diamine"Enantiomer. 5. 119-123 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] T.Oriyama, T.Hosoya, T.Sano: "Catalytic Asymmetrization of cis-2-Cydopentene-1,4-diol, Highly Efficient and Practical Synthesis of (R)4-4-Beyoylogy-2-cydopenten-1-one"Heteroeycles. 52. 1065-1069 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] T.Oriyama, H.Taguchi, D.Terakado, T.Sano: "Highly Efficient and Enantioselective Method for the Syn they is of Chiral Building Blocks Derived from wesc-1,3-Propauediols"Chem.Lett.. 26-27 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] T. Sano, K. Imai, K. Ohashi, and T. Oriyama: "Catalytic Asymmetric Acylation of Racemic Secondary Alcohols with Benzoyl Chloride in the Presence of a Chiral Diamine"Chem. Lett.. 265-266 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] T. Sano, K. Ohashi, andT. Oriyama: "Remarkably Fast Acylation of Alcohols with Benzoyl Chloride Promoted by TMEDA"Synthesis. 1141-1144 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] T. Sano and T. Oriyama: "Development of Catalytic Asymmetric Acylation of Alcohols in the Presence of a Chiral 1,2-Diamine"Journal of Synth. Org. Chem.. 57. 598-607 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] T. Sano, H, Miyata, and T. Oriyama: "Highly Efficient Kinetic Resolution or β-Halohydrins Catalyzed a Chiral 1,2-Diamine"Enantiomer. 5. 119-123 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] T. Oriyama, T. Hosoya, and T. Sano: "Catalytic Asymmetrization of cis-2-Cyclopentene-1,4-diol. Highly Efficient and Practical Synthesis of (R)-4-Benzoyloxy-2-cyclopenten-1-one."Heterocycles. 52. 1065-1069 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] T. Oriyama, H. Taguchi, D. Terakado, and T. Sano: "Highly Efficient and Enantioselective Method for the Synthesis of Chiral Building Blocks Derived from meso-1,3-Propanediols"Chem. Lett.. 26-27 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] T. Sano, K. Imai, K. Ohashi, T. Oriyama: "Catalytic Asymmetric Acylation of Raceomic Secoudary Alcohols with Beigoyl Chloride in the Presence of a Chiral Diamine"Chem. Lett.. 265-266 (1999)

    • Related Report
      2001 Annual Research Report
  • [Publications] T. Sano, K. Ohashi, T. Oriyama: "Reworkably Fast Acylation of Alcohols with Beigoyl Chloride Promoted by TMEDA"Synthesis. 1141-1144 (1999)

    • Related Report
      2001 Annual Research Report
  • [Publications] 佐野智文, 折山 剛: "キラルな1,2-ジアミンを用いるアルコール類の触媒的不斉アシル化の開発"有機合成化学協会誌. 57巻. 598-607 (1999)

    • Related Report
      2001 Annual Research Report
  • [Publications] T. Sano, H. Miyata, T. Oriyama: "Highly Ethicient Kinetic Resolution of β-Halohydrins Catalyzed by a Chiral 1,2-Diamine"Enantiomer. 5. 119-123 (2000)

    • Related Report
      2001 Annual Research Report
  • [Publications] T. Oriyama, T. Hosoya, T. Sano: "Catalytic Asymmetrization of cis-2-Cydopeuture-1,4-diol Highly Ethicient and Practical Synthesin of (R)-4-Benzoylory-2-cydopenten-houe"Heterocycles. 52. 1065-1069 (2000)

    • Related Report
      2001 Annual Research Report
  • [Publications] T. Oriyama, H. Taguchi, D. Terakado, T. Sano: "Highly Ethicient and Enantioselective Method for the Syutheske of Chiral Building Blocks Derived from the 1,3-Propanedicls"Chem. Lett.. 26-27 (2002)

    • Related Report
      2001 Annual Research Report
  • [Publications] T.Sauo,K.Imai,K.Ohashi,: "Catalytic Asymmetric Acylation of Racemate Secondary Alcohols with Benzoyl Chloride in the Presence of a Chiral Diamine"Chem.Kett.. 265-266 (1999)

    • Related Report
      2000 Annual Research Report
  • [Publications] T.Sauo,K.Chashi,and T.Oriyama: "Remarkably Fast Acylation of Alcohols with Benzoyl Chloride Promoted by TMEDA"Synthesis. 1141-1144 (1999)

    • Related Report
      2000 Annual Research Report
  • [Publications] 佐野智文,折山剛: "キラルなたマージアミンを用的アルコール類の触媒的不斉アシル化"有機合成化学協会誌. 57巻. 598-607 (1999)

    • Related Report
      2000 Annual Research Report
  • [Publications] T.Sauo,H.Miyata,and T.Oriyama: "Highly Efficinet Kinetic Resolution of β-Halohydrins Catalyzed by a Chiral 1,2-Diamine"Enantiomer. 5. 119-123 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] T.Oriyama,T.Hosoya,and T.Sauo: "Catalytic Asymmetrization of Cis-2-Cyclopentene-1,4thiol Highly Efficient and Pracfical Synthesis of (R)-4-Benzoylopy-2-cvclopentene-1-one"Heterocycles. 52. 1065-1069 (2000)

    • Related Report
      2000 Annual Research Report

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Published: 2000-04-01   Modified: 2016-04-21  

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