Cyanotrifluoromethylthiolation of Unactivated Olefins through Intramolecular Cyano Migration

A new protocol for the elusive cyanotrifluoromethylthiolation of unactivated olefins is described. A broad range of vicinal CF3S-substituted alkyl nitriles are furnished in good yields under mild reaction conditions. The intramolecular cyano migration strategy is harnessed for the trifluoromethylthiolation of alkenes for the first time, thus offering an efficient tool for the construction of alkyl trifluoromethylthioethers.