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.