Decarboxylative Perfluoroalkylation of Vinyl Bromides with Copper(I) Perfluorocarboxylato Complexes

A new decarboxylative perfluoroalkylation of vinyl bromides has been developed. The use of copper(I) trifluoroacetate complex (phen)Cu(O2CCF3) (1) and perfluorocarboxylate complexes [(phen)(2)Cu](O2CRF) (2; R-F=C2F5, n-C3F7, n-C4F9, n-C5F11) as reagents allows for the efficient synthesis of trifluoromethylated and perfluoroalkylated olefins, respectively. Vinyl bromides comprising a range of functionalities (e.g., methoxy, ester, nitrile, nitro, trifluoromethyl, chloride, and benzo[d][1,3]dioxole) were successfully accommodated. The decarboxylative trifluoromethylation and perfluoroalkylation reactions also proceeded with retention of the double-bond stereochemistry of alkenes after the reaction was completed.