K2S2O8-Mediated Selective Trifluoromethylacylation and Trifluoromethylarylation of Alkenes under Transition-Metal-Free Conditions: Synthetic Scope and Mechanistic Studies.

Abstract

A practical and efficient method for selective intramolecular radical trifluoromethylacylation and -arylation of alkenes with inexpensive CF3SO2Na and K2S2O8 in aqueous media has been developed, respectively, affording the highly chemoselective synthesis of CF3-functionalized chroman-4-ones and chromanes in satisfactory yields. Control experiments and DFT calculations indicate that the CF3SO2Na/K2S2O8 system is capable of trifluoromethylating the substrate of alkenes without a transition metal catalyst and the oxidation of CF3SO2Na to ·CF3 by K2S2O8 is involved in the rate-determining step.