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Development of Catalytic Asymmetric Synthesis of Optically Active beta-Hetero-alpha-amino Acids

Research Project

Project/Area Number 09650935
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field 有機工業化学
Research InstitutionKYOTO UNIVERSITY

Principal Investigator

KUWANO Ryoichi  Kyoto University, Graduate School of Engineering, Assistant Professor, 工学研究科, 助手 (20273477)

Project Period (FY) 1997 – 1998
Project Status Completed (Fiscal Year 1998)
Budget Amount *help
¥1,100,000 (Direct Cost: ¥1,100,000)
Fiscal Year 1998: ¥1,100,000 (Direct Cost: ¥1,100,000)
KeywordsCatalytic Asymmetric Synthesis / alpha-Amino Acid / beta-Hydroxy-alpha-amino Acid / alpha, beta-Diamino Acid / Piperazine-2-carboxylic Acid / Optically Active Compound / Rhodium Catalyst / Chiral Diphosphine Ligand / 不斉水素化 / α,β-ジアミノ酸 / 不斉アリル化 / パラジウム触媒 / 四級不斉炭素 / 不斉水素化反応 / ロジウム / 不斉配位子
Research Abstract

Optically active alpha-amino acids attached a hetero atom on the beta-carbon atom are important as not only constituents of many biologically active peptides but also chiral building blocks for syntheses of useful compounds. In this study, the author developed some new catalytic asymmetric syntheses of optically active beta-hetero-alpha-amino acids.
1. Stereoselective Synthesis of beta-Hetero-alpha-acetamldoacrylates. alpha-Acetamidoacrylates bearing a heterosubstituent at the beta-position were synthesized from the corresponding beta-keto-alpha- acetamidoacrylates. Both of the geometrical isomers were possible to be prepared with perfect stetreoselectivity.
2. Catalytic Asymmetric Hydrogenation of beta-Hetero-alpha-acetamidoacrylates. The beta-hetero-alpha- acetamidoacrylates thus obtained were hydrogenated with high enantioselectivity (up to 97% ee) by a chiral rhodium catalyst possessing a trans-chelating chiral diphosphine TRAP, which had been developed by the authors. threo- and erythro-beta-Hetero-alpha-amino acids were obtained with complete stereospecificity and high enantioselectivity from the (E)- and (Z)-substrates, respectively.
3. Catalytic Asymmetric Synthesis of Cyclic beta-Hetero-alpha-amino acids. The TRAP-rhodium catalysts were also effective for asymmetric hydrogenations of tetrahydropyrazine-2-carboxamides, giving (S)-piperazine-2-(N-tert-butyl)carboxamides with up to 97% ee, which are important for the synthesis of HIV protease inhibitor Crixivan. Of interest is that both of the enantiomers with high enantiomeric excess were possible to be obtained by two chiral catalysts derived from a single chiral source.

Report

(3 results)
  • 1998 Annual Research Report   Final Research Report Summary
  • 1997 Annual Research Report
  • Research Products

    (19 results)

All Other

All Publications (19 results)

  • [Publications] R.Kuwano: "Trans-Chelating Chiral Peralkyldiphosphine Ligands (R, R)-(S, S)-2, 2"-Bis[1-(dialkylphosphino)ethyl]-1, 1"-biferrocenes(AlkylTRAPs)and Their Transition Metal Complexes." Bulletin of the Chemical Society of Japan. 70. 2807-2822 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] R.Kuwano: "Asymmetric Aldol Reaction of 2-Cyanopropionates Catalyzed by Trans-Chelating Chiral Diphosphine Ligand TRAP-Rhodium Complex." Chemical Communications. 1998. 71-72 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] R.Kuwano: "Catalytic Asymmetric Synthesis of β-Hydroxy-α-amino Acids : Highly Enantioselective Hydrogenation of β-Oxy-α-acetamidoacrylates." The Journal of Organic Chemistry. 63. 3499-3503 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] R.Kuwano: "Asymmetric Hydrogenation of (E)-α, β-Bis(N-acylamino)acrylates Catalyzed by a Rhodium Complex with Trans-Chelating Chiral Diphosphine Ligand." Tetrahedron : Asymmetry. 9. 2773-2775 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] R.Kuwano: "Synthesis of Trans-Chelating Chiral Diphosphine Ligand with Only Planar Chirality and Their Application to Asymmetric Hydrosilylation of Ketones." Tetrahedron Letters. 40. 1327-1330 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] R.Kuwano: "Asymmetric Hydrogenation of 1, 4, 5, 6-Tetrahydropyrazine-2-(N-tert-butyl)carboxamide Catalyzed by Trans-Chelating Chiral Diphosphine-Rhodium Complexes." The Journal of Organic Chemistry. 64. 1232-1237 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Ryoichi Kuwano, et al.: ""Trans-Chelating Chiral Peralkyldiphosphine Ligands (R,R)-(S,S)-2,2"-Bis [1-(dialkylphosphino)ethyl]-1,1"-biferrocenes (AlkylTRAPs)and Their Transition Metal Complexes."" Bulletin of the Chemical Society of Japan. 70. 2807-2822 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Ryoichi Kuwano, et al.: ""Asymmetric Aldol Reaction of 2-Cyanopropionates Catalyzed by Trans-Chelating Chiral Diphoshine Ligand TRAP-Rhodium Complex."" Chemical Communications. 1998. 71-72 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Ryoichi Kuwano, et al.: ""Catalytic Asymmetric Synthesis of beta-Hydroxy-alpha-amino Acids : Highly Enantioselective Hydrogenation of beta-Oxy-alpha-acetamidoacrylates."" The Journal of Organic Chemistry. 63. 3499-3503 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Ryoichi Kuwano, et al.: ""Asymmetric Hydrogenation of (E)-alpha, beta-Bis (N-acylamino) acrylates Catalyzed by a Rhodium Complex with Trans-Chelating Chiral Diphosphine Ligand."" Tetrahedron : Asymmetry. 9. 2773-2775 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Ryoichi Kuwano, et al.: ""Synthesis of Trans-Chelating Chiral Diphosphine Ligand with Only Planar Chirality and Their Application to Asymmetric Hydrosilylation of Ketones, "" Tetrahedron Letters. 40. 1327-1330 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Ryoichi Kuwano, et al.: ""Asymmetric Hydrogenation of 1,4,5,6-Tetrahydropyrazine-2- (N-tert-butyl) carboxamide Catalyzed by Trans-Chelating Chiral Diphosphine-Rhodium Complexes."" The Journal of Organic Chemistry. 64. 1232-1237 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Ryoichi Kuwano, et al.: ""Catalytic Asymmetric Allylation of Prochiral Nucleophiles, alpha-Acetamido-beta-Ketoesters."" Journal of the American Chemical Society. 121(in press). (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] R.Kuwano: "Catalytic Asymmetric Synthesis of β-Hydroxy-α-amino Acids:Highly Enantiselective Hydrogenation of β-Oxy-α-acetamidoacrylates." The Journal of Organic Chemistry. 63. 3499-3503 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] R.Kuwano: "Asymmetric Hydrogenation of (E)-α,β-Bis(N-acylamino)acrylates Catalyzed by a Rhodium Complex with Trans-Chelating Chiral Diphosphine Ligand." Tetrahedron:Asymmetry. 9. 2773-2775 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] R.Kuwano: "Synthesis of Trans-Chelating Chiral Diphosphine Ligand with Only Planar Chirality and Their Application to Asymmetric Hydrosilylation of Ketones." Tetrahedron Letters. 40. 1327-1330 (1999)

    • Related Report
      1998 Annual Research Report
  • [Publications] R.Kuwano: "Asymmetric Hydrogenation of 1,4,5,6,-Tetrahydropyrazine-2-(N-tert-butyl)carboxamide Catalyzed by Trans-Chelating Chiral Diphosphine-Rhodium Complexes." The Journal of Organic Chemistry. 64. 1232-1237 (1999)

    • Related Report
      1998 Annual Research Report
  • [Publications] R.Kuwano: "Catalytic Asymmetric Allylation of Prochiral Nucleophiles,α-Acetamido-β-ketoesters." Journal of the American Chemical Society. 121(印刷中). (1999)

    • Related Report
      1998 Annual Research Report
  • [Publications] Ryoichi Kuwano: "Trans-Chelating Chiral Peralkyldiphosphine Ligands (R,R)-(S,S)-2,2"-Bis[1-(dialkylphosphino)ethyl]-1,1"-biferrocenes(AlkylTRAPs)and Their Transition Metal Complexes" Bulletin of the Chemical Society of Japan. 70. 2087-2822 (1997)

    • Related Report
      1997 Annual Research Report

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Published: 1998-04-01   Modified: 2016-04-21  

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