Nickel-catalyzed Thioester Transfer Reaction with sp 2 -Hybridized Electrophiles.

We report a thioacylation transfer reaction based on nickel-catalyzed C-C bond cleavage of thioesters with sp 2 -hybridized electrophiles. Aryl bromides, iodides, and alkenyl triflates can participate in thioester transfer reaction of aryl thioesters, affording a wide range of structurally diverse new thioesters in yields of up to 98% under mild reaction conditions. With this protocol, it is possible to construct alkenyl thioesters from the corresponding ketones through the generation of alkenyl triflates.