Chemoselective Ullmann Reaction of α-Trisubstituted Thioamides: Synthesis of Novel 2-Iminobenzothiolanes

New classes of unexplored benzo[b]thiolanes are synthesized from trisubstituted thioamides through copper-catalyzed intramolecular S-arylation of thioamides for the first time. This method provides good to excellent yields with fully controlled chemoselectivity. Unusually, iminobenzo[b]thiolanes are very stable under mild acidic conditions. A plausible mechanism is proposed for the chemoselective S-arylation process.