Copper-Catalyzed Regio- and Stereoselective Hydrothiolation of Allenamides, Enamides, and Ynamides

We report a simple protocol for the copper-catalyzed hydrothiolation of N-unsaturated precursors, i.e., allenamides, enamides, and ynamides, under mild conditions. This method proceeds with a low loading of a commercially available Cu(CH3CN)4PF6 catalyst and enables the room-temperature transformation of a wide range of aromatic and aliphatic thiols into allylic or vinylic thioethers, 1,3-dithioethers, and thioaminals with good regio- and stereoselectivity.