Development of enolate chemistry and total syntheses of bioactive natural products

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    Abstract

    Methodologies with chiral enolates including the stereoselective construction of the quaternary carbon, rearrangement of the vinylketene N,O-acetals, the remote stereoinduction with vinylketene silyl N,O-acetals, and the construction of 1,2-diols having the tertiary alcohol have been developed to apply to the natural product synthesis. Each isomer at the quaternary carbon has been synthesized from one enantiomer of α,β-unsaturated imide by choosing whether alkylation of the dienolate anion or rearrangement of the vinylketene N,O-acetal with MeAlCl 2. The vinylketene silyl N,O-acetals possessing the chiral auxiliary reacted with aldehydes in the presence of TiCl 4 to realize the stereocontrol at the y and 8 positions. Aldol reactions with lactate having the chiral auxiliary provided the 1,2-diols possessing the tertiary alcohol. The major stereoisomer depended on the chiral auxiliary and the protective group on the hydroxy group of lactate. These methodologies realized the short-step syntheses of natural products.

    Original languageEnglish
    Pages (from-to)24-37
    Number of pages14
    JournalYuki Gosei Kagaku Kyokaishi/Journal of Synthetic Organic Chemistry
    Volume67
    Issue number1
    Publication statusPublished - 2009 Jan

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    Keywords

    • Aldol reaction
    • Enolate
    • Ketene N,O-acetal
    • Natural product
    • Oxazolidinone
    • Quaternary carbon
    • Tertiary alcohol
    • Total synthesis
    • Vinylogous mukaiyama aldol reaction

    ASJC Scopus subject areas

    • Organic Chemistry

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