Highly Regioselective Rh-III-Catalyzed Thiolation of N-Tosyl Acrylamides: General Access to (Z)-beta-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(sp(2))-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 % Rh-III catalyst. In addition, diphenyl diselenide was also successfully applied to this reaction for the construction of (Z)-beta-alkenyl selenides under identical conditions.