Transition-Metal-Catalyzed Radical Cyclization: Copper-Catalyzed Cyclization of Allyl Trichloroacetates to Trichlorinated γ-Lactones

Hideo Nagashima, Koji Seki, Ozaki Nobuyasu, Hidetoshi Wakamatsu, Kenji Itoh, Yoichi Tomo, Jiro Tsuji

Research output: Contribution to journalArticle

99 Citations (Scopus)

Abstract

Cuprous salts in acetonitrile catalyzed the cyclization of allyl trichloroacetates to trichlorinated γ-lactones by way of an intramolecular atom-transfer radical cyclization. Various trichlorinated γ-lactones having a variety of alkyl substituents were prepared by this method. γ-Lactones were generally obtained as a singleproduct except the cyclization of methallyl trichloroacetate, which afforded a mixture of γ- and δ-lactones. The addition of a dichloroacetyl moiety and a chlorine atom to olefins was not stereospecific, Trichloroacetates of secondary allylic alcohols provided a mixture of diastereomers. The stereochemical outcome was dependent on the structure of the starting trichloroacetates; 2-cyclohexenyl trichloroacetate gave the corresponding cis-fused bicyclic lactone, whereas the reaction of acyclic trichloroacetates derived from l-buten-3-ol and its analogues generally provided the trans-substituted lactones. A mechanism of this reaction based on the stereochemical outcome is discussed.

Original languageEnglish
Pages (from-to)985-990
Number of pages6
JournalJournal of Organic Chemistry
Volume55
Issue number3
DOIs
Publication statusPublished - Jan 1 1990
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Organic Chemistry

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