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2004 Fiscal Year Final Research Report Summary

Development of Biocatalysts Using Organized Nano-reactors

Research Project

Project/Area Number 15550093
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Synthetic chemistry
Research InstitutionOKAYAMA UNIVERSITY

Principal Investigator

EMA Tadashi  OKAYAMA UNIVERSITY, Faculty of Engineering, Associate Professor, 工学部, 助教授 (20263626)

Co-Investigator(Kenkyū-buntansha) SAKAI Takashi  OKAYAMA UNIVERSITY, Faculty of Engineering, Professor, 工学部, 教授 (00170556)
KORENAGA Toshinobu  OKAYAMA UNIVERSITY, Faculty of Engineering, Assistant Professor, 工学部, 助手 (70335579)
Project Period (FY) 2003 – 2004
KeywordsBiocatalyst / Enzyme / Lipase / Immobilization / High temperature / Enantioselectivity / Kinetic resolution / Asymmetric reduction
Research Abstract

Kinetic resolution of 1,1-diphenyl-2-propanol was performed at high temperatures using a lipase immobilized on porous ceramics, Toyonite 200M. Reactions proceeded even at 120℃, giving enantiomerically pure ester product. In contrast, the reaction at 100℃ using the same lipase immobilized on Celite resulted in no reaction. The high-temperature biocatalysis in supercritical CO_2 medium at 80℃ gave 42% conversion with an E value of 211. The lipase-catalyzed acylation of a secondary alcohol having tetraphenylporphyrin as a substituent proceeded at 60℃ most efficiently, giving enantiomerically pure ester and alcohol.
Lipase mutant was immobilized on the porous ceramics to study how far the enantioselectivity can be controlled on the basis of a reaction mechanism. Substitution of some amino acid residue in the proximity of the active site with another one resulted in a change in enantioselectivity, as expected. Thermodynamic parameters suggested that the change in enantioselectivity was driven by the change in activation enthalpy.
A new method for the prediction of absolute configurations of secondary alcohols using immobilized lipase was invented. Using the E values for two kinds of 1-substituted ethanols having different substituents, the E value for another secondary alcohol having the two substituents on both sides was predicted and determined. The experimental results for 19 out of 20 examples were consistent with the prediction.
A carbonyl reductase obtained with recombinant E.coli was immobilized on the porous ceramics, which unfortunately showed no remarkable effect. Rather, whole-cell reductions using E.coli coexpressing two genes encoding the carbonyl reductase and a glucose dehydrogenase gave optically active alcohols much more easily and efficiently. Highly enantioselective asymmetric reductions were achieved, and 8 out of 16 ketones were reduced to optically active alcohols with >98% ee.

  • Research Products

    (6 results)

All 2005 2004 2003

All Journal Article (6 results)

  • [Journal Article] Lipase-Catalyzed Resolution of (2R^*,3S^*)- and (2R^*,3R^*)-3-Methyl-3-phenyl-2-aziridinemethanol at Low Temperatures and Determination of the Absolute Configurations of the Four Stere oisomers.2005

    • Author(s)
      Sakai, T., Liu, Y., Ohta, H., Korenaga, T., Ema, T.
    • Journal Title

      The Journal of Organic Chemistry 70

      Pages: 1369-1375

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Asymmetric Reduction of a Variety of Ketones with a Recombinant Carbonyl Reductase : Identification of the Gene Encoding a Versatile Biocatalyst.2005

    • Author(s)
      Ema, T., Yagasaki, H., Okita, N., Nishikawa, K., Korenaga, T., Sakai, T.
    • Journal Title

      Tetrahedron : Asymmetry 16

      Pages: 1075-1078

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Lipase-Catalyzed Resolution of (2R^*,3S^*)-and (2R^*,3R^*)-3-Methyl-3-phenyl-2-aziridinemethanol at Low Temperatures and Determination of the Absolute Configurations of the Four Stereoisomers.2005

    • Author(s)
      Sakai, T., Liu, Y., Ohta, H., Korenaga, T., Ema, T.
    • Journal Title

      The Journal of Organic Chemistry 70

      Pages: 1369-1375

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Asymmetric Reduction of a Variety of Ketones with a Recombinant Carbonyl Reductase : Identification of the Gene Encoding a Versatile Biocatalyst.2005

    • Journal Title

      Tetrahedron : Asymmetry 16

      Pages: 1075-1078

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] The Effect of Temperature on the Lipase-Catalyzed Asymmetric Protonation of 1-Acetoxy-2-methylcyclohexene Giving (R)-2-Methylcyclohexanone.2004

    • Author(s)
      Sakai, T., Matsuda, A., Tanaka, Y., Korenaga, T., Ema, T.
    • Journal Title

      Tetrahedron : Asymmetry 15

      Pages: 1929-1932

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Highly Enantioselective Lipase-Catalyzed Reactions at High Temperatures up to 120℃ in Organic Solvent.2003

    • Author(s)
      Ema, T., Kageyama, M., Korenaga, T., Sakai, T.
    • Journal Title

      Tetrahedron : Asymmetry 14

      Pages: 3943-3947

    • Description
      「研究成果報告書概要(和文)」より

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Published: 2006-07-11  

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