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(sp³)-S or C(sp²)-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.