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

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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

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Cyclization
Lactones
Transition metals
Copper
Atoms
Chlorine
Alkenes
Salts

All Science Journal Classification (ASJC) codes

  • Organic Chemistry

Cite this

Transition-Metal-Catalyzed Radical Cyclization : Copper-Catalyzed Cyclization of Allyl Trichloroacetates to Trichlorinated γ-Lactones. / Nagashima, Hideo; Seki, Koji; Nobuyasu, Ozaki; Wakamatsu, Hidetoshi; Itoh, Kenji; Tomo, Yoichi; Tsuji, Jiro.

In: Journal of Organic Chemistry, Vol. 55, No. 3, 01.01.1990, p. 985-990.

Research output: Contribution to journalArticle

Nagashima, Hideo ; Seki, Koji ; Nobuyasu, Ozaki ; Wakamatsu, Hidetoshi ; Itoh, Kenji ; Tomo, Yoichi ; Tsuji, Jiro. / Transition-Metal-Catalyzed Radical Cyclization : Copper-Catalyzed Cyclization of Allyl Trichloroacetates to Trichlorinated γ-Lactones. In: Journal of Organic Chemistry. 1990 ; Vol. 55, No. 3. pp. 985-990.
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N2 - 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.

AB - 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.

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