Highly Regioselective RhIII-Catalyzed Thiolation of N-Tosyl Acrylamides: General Access to ( Z)-β-Alkenyl Sulfides.

A regioselective rhodium-catalyzed thiolation of N-tosyl acrylamides with readily available disulfides has been developed. Through N-tosylamide-assisted activation of the alkenyl C(sp2)-H bond, a series of ( Z)-alkenyl sulfides were constructed in moderate to excellent yields with good tolerance of functional groups. Turnover numbers (TONs) of up to 7100 were obtained utilizing 0.01 mol % RhIII catalyst. In addition, diphenyl diselenide was also successfully applied to this reaction for the construction of ( Z)-β-alkenyl selenides under identical conditions.