Site-Selective Olefinic C-H Cyanation via Alkenyl Sulfonium Salts

A chemo- and regioselective olefinic C–H cyanation strategy was developed via alkenyl sulfonium salts with CuCN, affording alkenyl nitriles by a site-selective interrupted Pummerer activation/palladium-catalyzed olefinic C(sp 2 )–S cyanation sequence.