PhI(OAc)2-Mediated Regioselective Hydrothiolation of Allenamides with Thiophenol via a Radical Process: Synthesis of Vinyl Sulfides.

Abstract

An efficient PhI(OAc)2-mediated regioselective hydrothiolation of allenamides with thiophenol via a radical process was developed to create a workable route to vinyl sulfides. The reaction exhibits a good functional group tolerance and high efficiency, affording the products in good to excellent yields. Mechanistic investigations indicated that the radical cascade proceeds through an allyl radical intermediate, which is formed via the addition of the PhS radical to the central carbon of allenamides. Moreover, the reaction was also efficient with selenophenol, providing the corresponding product, vinyl selenide, in a 99% yield.