Copper-Catalyzed Divergent C–S Bond Cleavage of Vinylsulfonium Salts: Controllable Phosphoryloxylation and Phosphinoylation

A facile copper-catalyzed system enables controllable phosphoryloxylation and phosphinoylation of vinylsulfonium salts with P(O)–H compounds. Reaction divergence is achieved by employing distinct copper catalysts to steer the selective cleavage of either the C(sp 3 )–S or C(sp 2 )–S bond of vinylsulfonium salts. This protocol features mild conditions, a short reaction time, a broad substrate scope, and gram-scale applicability. Based on collective evidence from control experiments, plausible reaction pathways for both transformations are proposed.