Chemo-Enzymatic合成法によるジフルオロメチレン基を有するキラル化合物の合成  [in Japanese] Asymmetric Synthesis of Novel gem-Difluorinated Compounds Using Chemo-Enzymatic Methodology  [in Japanese]

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Abstract

Asymmetric synthesis of two types of partly difluorinated compounds has been accomplished based on the chemo-enzymatic reaction strategy. Optically active 1, 1-difluoro-2, 3- (bishydroxymethyl) cyclopropane has been synthesized through lipase-catalyzed reaction; prochiral diacetate of <I>cis</I>-1, 1-difluoro-2, 3-bis (hydroxymethyl) cyclopropane was converted to the corresponding monoacetate through <I>Alcaligenes</I> sp. lipase-catalyzed hydrolysis with >99% enantiomeric excess. Racemic acetate of <I>trans</I>-1, 1-difluoro-2, 3-bis (hydroxymethyl) cyclopropane was resolved by <I>Pseudomonas</I> sp. lipase-catalyzed hydrolysis successfully. Lipase-catalyzed reaction was employed to resolve bis-difluorocyclopropane derivatives; the first synthesis of optically pure (<I>trans</I>, <I>trans</I>) -2, 2, 5, 5-tetrafluoro-1, 6-bis (hydroxymethyl) bicyclopropane has thus been accomplished. Carbon radicals from allyl O-trimethylsilyl-α-bromo-α, α-difluoroacetal can cyclize onto the olefinic part regiospecifically to give γ-lactols in good yield. The lactols are then converted to the corresponding α, α-difluoro-γ-lactones. Systematic synthesis of multifluorinated-α, α-difluoro-γ-lactones has been accomplished through intramolecular radical cyclization as a key reaction. The synthesis of difluorinated analogue of an insect sex pheromone has been accomplished through intramolecular radical cyclization and lipase-catalyzed reaction.

Journal

  • Journal of Synthetic Organic Chemistry, Japan

    Journal of Synthetic Organic Chemistry, Japan 58(4), 316-323, 2000-04-01

    The Society of Synthetic Organic Chemistry, Japan

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Codes

  • NII Article ID (NAID)
    10008819788
  • NII NACSIS-CAT ID (NCID)
    AN0024521X
  • Text Lang
    JPN
  • Article Type
    ART
  • ISSN
    00379980
  • NDL Article ID
    5342121
  • NDL Source Classification
    ZP11(科学技術--化学・化学工業--有機化学・有機化学工業)
  • NDL Call No.
    Z17-256
  • Data Source
    CJP  NDL  J-STAGE 
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