Nickel-Catalyzed Desulfurizative Sonogashira Cross-Coupling of Terminal Alkynes with Alkenylsulfonium Salts

A new protocol for C(sp²)-C(sp) bond formation via the nickel-catalyzed desulfurizative Sonogashira cross-coupling reaction involving C(sp²)-S bond cleavage with alkenylsulfonium salts as an electrophilic coupling partner is described. The reaction proceeded smoothly for preparation of (<i>E</i>)-conjugated enynes with a broad functional group tolerance under the optimized conditions. Notably, direct alkene alkynylation can be achieved through a one-pot process without the isolation of alkenylsulfonium salts. The synthetic utility of this protocol is further demonstrated by its applicability in scale-up reaction and late-stage modification of complex bioactive scaffolds.