Heteroatom-guided torquoselective olefination of α-oxy and α-amino ketones via ynolates

Mitsuru Shindo, Takashi Yoshikawa, Yasuaki Itou, Seiji Mori, Takeshi Nishii, Kozo Shishido

Research output: Contribution to journalArticlepeer-review

40 Citations (Scopus)

Abstract

Ynolates were found to react with α-alkoxy-, α-siloxy-, and α -aryloxyketones at room temperature to afford tetrasubstituted olefins with high Z selectivity. Since the geometrical selectivity was determined in the ring opening of the β-lactone enolate intermediates, the torquoselectivity was controlled by the ethereal oxygen atoms. From experimental and theoretical studies, the high Z selectivity is in duced by orbital and steric interactions rather than by chelation. In a similar manner, α-dialkylamino ketones provided olefins with excellent Z selectivity. These products can be easily converted into multisubstituted butenolides and γ-butyrolactams in good yield.

Original languageEnglish
Pages (from-to)524-536
Number of pages13
JournalChemistry - A European Journal
Volume12
Issue number2
DOIs
Publication statusPublished - Dec 23 2005

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Organic Chemistry

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