A Reaction of Triazoles with Thioesters to Produce β-Sulfanyl Enamides by Insertion of an Enamine Moiety into the Sulfur-Carbonyl Bond

N-Sulfonyl-1,2,3-triazoles react with thioesters in the presence of a rhodium(II) catalyst to produce β-sulfanyl enamides in a stereoselective manner. The reaction proceeds through generation of an α-imino rhodium carbene complex, nucleophilic addition of the sulfur atom of a thioester onto the carbenoid carbon atom, and subsequent intramolecular migration of the acyl group from the sulfur atom to the imino nitrogen atom. The method is successfully applied to a ring-expansion reaction of thiolactones, thus leading to the formation of sulfur-containing lactams.