Direct Assembly of Privileged α-CF ₃ Allylamines via Photoinduced Pd-Catalyzed C–H Aminoalkylation of Alkenes

α-CF₃ allylamines are valuable scaffolds in pharmaceuticals, agrochemicals, and materials science, yet efficient synthetic methods remain scarce. Herein, we report a photoinduced palladium-catalyzed C-H aminoalkylation of alkenes for the direct assembly of privileged α-CF₃ allylamines. This redox-neutral method utilizes readily available alkenes and <i>N</i>-trifluoroethyl hydroxylamine reagents under mild conditions, enabling efficient radical-mediated coupling via a proposed mechanism involving Pd(0)*-triggered single-electron transfer (SET), 1,2-HAT, and Heck-type addition. The reaction exhibits a broad substrate scope and excellent functional group compatibility and can be applied to late-stage functionalization of complex molecules, including pharmaceuticals and natural product derivatives. Additionally, the strategy extends to other fluoroalkyl and ester substituents, offering a versatile platform for synthesizing bioactive α-fluoroalkyl allylamines and substituted amino acid derivatives.