Development of enolate chemistry and total syntheses of bioactive natural products

    研究成果: Article

    15 引用 (Scopus)

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    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.

    元の言語English
    ページ(範囲)24-37
    ページ数14
    ジャーナルYuki Gosei Kagaku Kyokaishi/Journal of Synthetic Organic Chemistry
    67
    発行部数1
    出版物ステータスPublished - 2009 1

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    Acetals
    Biological Products
    Lactic Acid
    Carbon
    Alcohols
    Imides
    Stereoisomerism
    Enantiomers
    Alkylation
    Aldehydes
    Isomers
    Anions

    ASJC Scopus subject areas

    • Organic Chemistry

    これを引用

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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.",
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    KW - Aldol reaction

    KW - Enolate

    KW - Ketene N,O-acetal

    KW - Natural product

    KW - Oxazolidinone

    KW - Quaternary carbon

    KW - Tertiary alcohol

    KW - Total synthesis

    KW - Vinylogous mukaiyama aldol reaction

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