Photocatalytic Remote Oxyfluoroalkylation of Heteroalkynes: Regio-, Stereo-, and Site-Selective Access to Complex Fluoroalkylated ()-Alkenes.

A visible-light-induced remote oxyfluoroalkylation, including ketofluoroalkylation and hydroxytrifluoromethylation, of heteroalkynes is developed with dimethyl sulfoxide (DMSO) and HO as the oxygen source, respectively. It provides a facile access to complex fluoroalkylated ()-alkenes in satisfactory yields with excellent regio-, stereo-, and site-selectivity. The reaction involves an uncommon vinyl radical-induced intermolecular C(sp)-H functionalization, thus offering a good platform for the development of remote difunctionalization of alkynes.