Development of enolate chemistry and total syntheses of bioactive natural products

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15 Citations (Scopus)

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 MeAlCl2. The vinylketene silyl N,O-acetals possessing the chiral auxiliary reacted with aldehydes in the presence of TiCl4 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
DOIs
Publication statusPublished - 2009 Jan

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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