Trifluoromethylfluorosulfonylation of Unactivated Alkenes Using Readily Available Ag(O2CCF2SO2F) and N‐Fluorobenzenesulfonimide

Presented is a novel intermolecular radical trifluoromethylfluorosulfonylation of unactivated alkenes under mild reaction conditions with good functional‐group tolerance in the most atom‐economic manner by using readily available Ag(O2CCF2SO2F) and N‐fluorobenzenesulfonimide (NFSI). Both the trifluoromethyl and sulfonyl groups in the products originate from Ag(O2CCF2SO2F). Making it functional: The title reaction proceeds using the readily available Ag(O2CCF2SO2F) and N‐fluorobenzenesulfonimide (NFSI) under mild reaction conditions, and features good functional‐group tolerance. The CF3 group in the product originates from a AgCF3 species formed from Ag(O2CCF2SO2F), and the in situ generated SO2 is trapped and converted into a sulfonyl group, thus demonstrating the atom economy of the reaction.