Late‐Stage Modification of Drugs via Alkene Formal Insertion into Benzylic C−F Bond

C-F insertion of carbon-atom units is underdeveloped although it poses significant potential applications in both drug discovery and development. Herein, we report a photocatalytic protocol for late-stage modification of trifluoromethyl aromatic drugs involving formal insertion of abundant alkene feedstocks into a benzylic C-F bond selectively. This redox-neutral transformation features mild conditions and extraordinary functional group tolerance. Preliminary studies are consistent with this transformation involving a radical-polar crossover pathway. Additionally, it offers an alternative strategy for difunctionalization of alkenes via quenching of the carbocation intermediate with nucleophiles other than external fluoride.