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Development of Enzymatic Method for Asymmetric Induction and Its Application for Natural Products Synthesis

Research Project

Project/Area Number 03805075
Research Category

Grant-in-Aid for General Scientific Research (C)

Allocation TypeSingle-year Grants
Research Field 有機工業化学
Research InstitutionSHIZUOKA UNIVERSITY

Principal Investigator

TAKABE Kunihiko  Faculty of Engineering, Department of Applied Chemistry, Associate Professor, 工学部, 助教授 (30022239)

Project Period (FY) 1991 – 1992
Project Status Completed (Fiscal Year 1992)
Budget Amount *help
¥1,600,000 (Direct Cost: ¥1,600,000)
Fiscal Year 1992: ¥400,000 (Direct Cost: ¥400,000)
Fiscal Year 1991: ¥1,200,000 (Direct Cost: ¥1,200,000)
KeywordsChemoenzymatic Process / Bakers' Yeast / Asymmetric Reduction / Lipase / Transesterification / alpha-Tocopherol / Variabilin / Autoregulator / リパ-ゼ / 不斉エステル交換反応 / 立体制御 / Aーファクタ- / αートコフェロ-ル
Research Abstract

1. Synthesis of chiral lactones using bakers' yeast Bakers' yeast reduction of 3-alkylated-gamma-butenolides gave chiral gamma-butanolides with high optical purity in good yield. Bakers' yeast reduction of 3-phenylthiomethylbutenolide afforded (R)-3-phenylthio-methyl-gamma-butanolide (99%ee), a versatile chiral building block for terpene synthesis. Similar reaction of 3-benzyloxymethyl-gamma-butenolide gave (S)-3-benzyloxymethylbutanolide (95%ee), and its transformation to factor-I, the autoregulator of S. viridocchromogenes, was also examined.
2. Asymmetric synthesis of natural alpha-tocopherol The formal synthesis of (2R,4'R,8'R)-alpha-tocopherol was achieved using chemoenzymatic process. The chroman part was synthesized via lipase-catalyzed hydrolysis of prochiral 1,3-diacetate and the optical purity of the monoester obtained was 67%ee. On the other hand, the C_<15> side chain was obtained in 95%ee via lipase-catalyzed transesterification of C_5 prochiral 1,3-diol.
3. Asymmetric synthesis of variabilin, furanosesterterpene in sponge The first synthesis of antibacterial (S)-variabilin, isolated from Ircinia variabilis was accomplished via two routes by lipase-catalyzed asymmetric transesterification of prochiral 1,3-diols. The optical purity in asymmetric induction to 2-hydroxymethyl-4-phenylthio-1-butanol, the key intermediate of variabilin synthesis, was 99%ee.
4. Asymmetric synthesis of the autoregulator of antibiotics in Streptomyces Virginia butanolide C, virginiamycin inducing factor of S. virgiae, was accomplished via chemoenzymatic process. In the course of this work, it was found that lipase-catalyzed transesterification of prochiral 2-amidoethyl-1,3-propanediols gave the chiral monoesters with high optical purity and the absolute configuration of the monoester was dependent on the amide group.

Report

(3 results)
  • 1992 Annual Research Report   Final Research Report Summary
  • 1991 Annual Research Report
  • Research Products

    (9 results)

All Other

All Publications (9 results)

  • [Publications] 高部 国彦: "Asymmetrie Reduction of 3-Hydroxymethylbutenlide Derivatives by Bakers′Yeast:A New Apprach to Synthesis of Factor-I" Tetrahedron:Asymmetry. 3. 1385-1386 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] 高部 国彦: "Bakers′Yeast Reduction of 3-Phenylthiomethy1-2-butenolide and Its Derivatives:Synthesis of Versatile Chiral C5-Building Blocks for Terpenoids Synthesis" Tetrahedron:Asymmetry. 3. 1399-1400 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] 高部 国彦: "Chemoenzymatic Synthesis of Optically Active Tocopherol" Bioorganic&Medicinal Chemistry Letters. 2. (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] K. Takabe: "Asymmetric reduction of 3-hydroxymethylbutenolide Derivatives by bakers' yeast: A new approach to the synthesis of factor-I" Tetrahedron: Asymmetry. 3(11). 1385-1386 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] K. Takabe: "Bakers' yeast reduction of 3-phenylthiomethyl-2-butenolide and its derivatives: Synthesis of versatile chiral C5-building blocks for terpenoids synthesis" Tetrahedron: Asymmetry. 3(11). 1399-1400

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] K. Takabe: "Chemoenzymatic synthesis of optically active alpha-tocopherol sode chain" Bioorganic & Medical Chemistry Letters. 2(2). (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] 高部 圀彦: "Asymmetric Reduction of 3-Hydroxymethylbutenolide Derivatives by Bakers' Yeast:A New Approach to the Synthesis of Factor-1" Tetrahedron: Asymmetry. 3. 1385-1386 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] 高部 圀彦: "Bakers' Yeast Reduction of 3-Phenylthiomethy1-2-butenolide and Its Derivatives: Synthesis of Versatile Chiral C5-Building Blocks for Terpenoids Synthesis" Tetrahedron: Asymmetry. 3. 1399-1400 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] 高部 圀彦: "Chemoenzymatic Synthesis of Optically Active Tocopherol Side Chain" Bioorganic & Medicinal Chemistry Letters. 2. (1993)

    • Related Report
      1992 Annual Research Report

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Published: 1991-04-01   Modified: 2016-04-21  

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