Tributylstannane-Mediated Cyclization of Thionocarboxylic Acid Derivatives

Abstract

Cyclization reactions of various thionoesters and thioamides involving the addition of tri-n-butylstannyl radical to a thiocarbonyl group and intramolecular addition of the resulting radical to a carbon-carbon multiple bond was studied. Dithiocarbonate and (imidazolyl)thiocarbonyl derivatives of homoallylic alcohols gave α-substituted γ-thionobutyrolactones. The reaction is highly dependent on the substitution pattern on the double bond, a high yield of cyclic products being obtained only when the double bond is activated and unhindered. (Z)-4-Phenylbut-3-enyl thionobenzoate afforded 4,5-dihydro-2-phenyl-3-benzylfuran in low yield. In reactions involving a thioamide group, good yields of cyclic products were obtained only from compounds in which the electron density on the nitrogen atom is decreased by an electron attracting group. Cyclization of 1-((E)-4-phenylbut-3-en-1-yl)-5-thioxopyrrolidin-2-one (23) afforded 1-aza-4-benzylbicyclo[3.3.0]oct-4-en-8-one (33).

Document Type

Article

DOI

https://doi.org/10.1021/jo00051a024

Publication Date

12-1-1992

Journal Title

Journal of Organic Chemistry

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