α-置換セリン誘導体の不斉合成  [in Japanese] Asymmetic Synthesis of α-Substituted Serines  [in Japanese]

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Abstract

Novel methodologies for the preparation of a-substituted serines are described. A newly designed bislactim ether, ethyl (5<I>S</I>) - or (5<I>R</I>) -3, 6-diethoxy-2, 5-dihydro-5-isopropyl-2-pyrazinecarboxylate, was treated with base or Lewis acid-tertiary amine to generate an enolate or enaminate (imine anion, metalloenamine). Alkylation or aldol-type reaction with the resultant enolate or enaminate proceeded in a highly diastereoselective manner to give the corresponding products. Reduction of these diastereomers followed by hydrolysis afforded the desirable α-substituted serines. The highly enantioselective aldol-type reaction of an achiral bislactim ether, ethyl 3, 6-diethoxy-2, 5-dihydro-2-pyrazinecarboxylate, was also achieved by employing Sn (OSO<SUB>2</SUB>CF<SUB>3</SUB>) <SUB>2</SUB>-triethylamine in the presence of a catalytic amount of (-) -sparteine. Interestingly, the stereoselective outcome of the Sn (II) -mediated reaction differed from that of the Mg (II) -mediated one in the aldol-type reaction of the bislactim ethers with aliphatic aldehydes.<BR>On the other hand, chemoenzymatic synthesis of enantiomerically pure α-substituted serines must also be a convenient and useful procedure. Porcine liver esterase (PLE) or rabbit liver esterase (RLE) catalyzed hydrolysis of the pro-S ester group of diethyl α-alkyl-α- (benzyloxycarbonylamino) malonates to afford (<I>R</I>) -ethyl α-alkyl-α- (benzyloxycarbonylamino) malonates each in excellent enantiomeric excess. Enantiodivergent reductions of these acid esters readily furnished both the corresponding enantiomeric α-substituted serines.<BR>Finally, the application of these methodologies mentioned above to a total synthesis of ISP-I (a potent immunosuppressant) and (+) -conagenin (a low molecular weight immunomodulator) is described.

Journal

  • Journal of Synthetic Organic Chemistry, Japan

    Journal of Synthetic Organic Chemistry, Japan 58(8), 756-765, 2000-08-01

    The Society of Synthetic Organic Chemistry, Japan

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Codes

  • NII Article ID (NAID)
    10008821254
  • NII NACSIS-CAT ID (NCID)
    AN0024521X
  • Text Lang
    JPN
  • Article Type
    Journal Article
  • ISSN
    00379980
  • NDL Article ID
    5431989
  • 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  CJPref  NDL  J-STAGE 
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