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Synthetic Studies on Substituted Citrate Natural Products based on the Cinchona Alkaloid-Catalyzed Asymmetric Baylis-Hillman reaction

Research Project

Project/Area Number 13672221
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Chemical pharmacy
Research InstitutionTohoku University (2002)
Nagasaki University (2001)

Principal Investigator

IWABUCHI Yoshiharu  Tohoku University, Graduate School of Pharmaceutical Sciences, Professor, 大学院・薬学研究科, 教授 (20211766)

Co-Investigator(Kenkyū-buntansha) HATAKEYAMA Susumi  Nagasaki University, Graduate School of Biomedical Sciences, Professor, 大学院・医歯薬学総合研究科, 教授 (20143000)
Project Period (FY) 2001 – 2002
Project Status Completed (Fiscal Year 2002)
Budget Amount *help
¥3,700,000 (Direct Cost: ¥3,700,000)
Fiscal Year 2002: ¥1,100,000 (Direct Cost: ¥1,100,000)
Fiscal Year 2001: ¥2,600,000 (Direct Cost: ¥2,600,000)
KeywordsBaylis-Hillman reaction / asymmetric synthesis / asymmetric catalvsis / substituted citrate / tertiary amines / nucleophilic catalysis / cinchona alkaloids / Baylis-Hillman反応
Research Abstract

We have previously developed a highly enantioselective asymmetric BaylisHillman reaction which allows us to construct a wide variety of (α-methylene-β-hydroxy)esters with highly optical purity (>90% ee). The reaction relies upon the combinatorial use of two important reagents, 1,1,1,3,3,3-hexafluoroisopropyl acrylate as an activated alkene and (3R, 8K,,9S)-10,11-dihydro-3,9-epoxy-6'-hydroxy-cinchonane as a chiral, nucleophilic amine catalyst. In this research program, we have established the synthetic utility of the reaction system in a practical sense, by demonstrating its applicability to the crucial step in total syntheses of biologically active natural products, including a potent immunosuppressant amino acid, (-)-mycestericin E, and a novel proteasome inhibitor epopromycin B. The reaction was found to be applicable to α-keto ester-type substrates to furnish the corresponding α-methylene-β-alkoxycatbonyl-β-hydroxy)esters in good chemical yield with modest enantioselectivity. These reaction products should serve as useful synthons for the preparation of a series of substituted citratetype compounds.

Report

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

    (9 results)

All Other

All Publications (9 results)

  • [Publications] Y.Iwabuchi, M.Furukawa, T.Esumi, S.Hatakeyama: "An enantio-and stereocontrolled synthesis of (-)-mycestericin E via cinchona alkaloid-catalyzed asymmetric Baylis-Hiliman reaction"ChemicalCommunications. 19. 2030-2031 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Y.Iwabuchi, T.Sugihara, T.Esumi, S.Hatakeyama: "An enantio-and stereocontrolled route to epopromycin B via cinchoha alkaloid catalyzed Baylis-Hillman reaction"Tetrahedron Letters. 42・44. 7867-7871 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Y.Iwabuchi, S.Hatakeyama: "Recent progress in the Morita-Baylis-Hillman reaction"Journal of Synthetic Organic Chemistry, Japan. 60・1. 2-14 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Y.Iwabuchi, M.Furukawa, T.Esumi, S.Hatakeyama: "An enantio-and stereocontrolled synthesis of (-)-mycestericin E via cinchona alkaloid-catalyzed asymmetric Baylis-Hillman reaction"Chemical Communications. 2030-2031 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Y.Iwabochi, T.Sngihara, T.Esumi, S.Hatakeyama: "An enantio- and stereocontrolled route to epopromycin B via cinchoha alkaloid catalyzed Baylis-Hillman reaction"Tetrahedron Letters. 42. 7867-7871 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Y.Iwabuchi, S.Haiakeyama: "Recent progress in the Morita-Baylis-Hillman reaction"Journal of Synthetic Organic Chemistry, Japan. 60. 2-14 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Y.Iwabuchi, S.Hatakeyama: "Recent progress in the Morita-Baylis-Hillman reaction"Journal of Synthetic Organic Chemistry, Japan. 60・1. 2-14 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Y.Iwabuchi, M.Furukawa, T.Esumi, S.Hatakeyama: "An enantio-and stereocontrolled synthesis of (-)-mycestericin E via cinchona alkaloid-catalyzed asymmetric Baylis-Hillman reaction"ChemicalCommunications. 19. 2030-2031 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Y.Iwabuchi, T.Sugihara, T.Esumi, S.Hatakeyama: "An enantio-and stereocontrolled route to epopromycin B via cinchona alkaloid catalyzed Baylis-Hillman reaction"Tetrahedron Letters. 42・44. 7867-7871 (2001)

    • Related Report
      2001 Annual Research Report

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

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