Photoinduced Defluorinative Alkylamination of Alkenes with Trifluoromethylated Arenes and Anilines

Selective defluorinative functionalization of inexpensive and readily available trifluoromethylated arenes represents a promising synthetic strategy for accessing pharmaceutically valuable fluorinated motifs. However, such transformations typically rely on transition-metal catalysts, and the development of sustainable, metal-free catalytic systems, particularly for three-component coupling reactions, remains scarce. Herein, we report a transition-metal-free, photoinduced defluorinative alkylamination of alkenes. This reaction utilizes inexpensive and readily available trifluoromethylarenes and anilines as coupling partners to afford a diverse array of γ,γ -difluoroalkylamines, valuable bioisosteres of β -amino ketones, which are prevalent motifs in pharmaceuticals and biologically active compounds. The transformation proceeds efficiently under blue light irradiation in the presence of an organic photosensitizer. Mechanistic studies indicate that the reaction proceeds via a sequential single-electron transfer (SET) pathway, culminating in C–N bond formation with anilines.