Meng-Qi Shen, Jie-Yang Dong, Qingyu Lin, Qi Zhang, Ming‐Chen Fu
The α-C(sp 3 )–H alkenylation of amines provides a direct and efficient approach for allylamine synthesis, but it is typically limited by harsh reagents and the need for preactivated alkenes. Here we present a visible-light-induced palladium-catalyzed radical relay Heck reaction that enables the direct α-C(sp 3 )–H alkenylation of amines with high selectivity. A key innovation is a hybrid ligand system that combines monodentate phosphine and bidentate nitrogen ligands─marking the first use of bidentate nitrogen ligands in photoinduced Pd catalysis. This design effectively suppresses competitive β-H elimination by stabilizing the alkene insertion process, while imposing an endergonic barrier for monodentate phosphine ligand dissociation. Late-stage α-C(sp 3 )–H alkenylation of complex bioactive amines, and streamlined synthesis of two nature products, caulophyllumine B and norruspoline, underscore significant synthetic potential in synthetic organic chemistry and biomedicine.