Controllable Single and Double C–F Bond Cleavage for Divergent Synthesis of Fluorinated Pyrroles and γ-Lactams

Direct C–F bond functionalization of readily accessible polyfluorinated compounds represents an efficient strategy for constructing complex fluorine-containing molecules. While the controllable cleavage of C–F bonds with high chemoselectivity in perfluoroalkyl groups has posed a significant challenge, we present a photocatalytic method that allows for switchable, substrate-controlled cleavage of single or double C(sp3)-F bonds in perfluoroalkyl iminosulfide, which can be conveniently prepared in one pot from readily available perfluoro carboxylic acids. This chemodivergent strategy enables the production of a variety of rarely accessed fluorinated pyrroles and γ-lactams with high chemoselectivity. This method demonstrates a broad substrate scope and excellent tolerance for functional groups. The successful applications of this methodology to pharmacologically relevant molecules underscore its synthetic potential. Furthermore, the synthesis of a compound containing a trifluoromethyl group and a fluorine atom unit, which serves as an analog useful for preventive or therapeutic applications in psychological disorders, illustrates the utility of this reaction. Mechanistic studies have been performed to elucidate the reaction pathway.