Ligand-Regulated Metallaphotoredox Aminoarylation for the Valorization of Feedstock Alkenes.

N-(Hetero)aryl-substituted arylethylamine derivatives are privileged scaffolds with broad biological activity for drug discovery. However, current synthetic approaches are limited by reliance on prefunctionalized substrates, multistep protocols, and harsh conditions. Free N-H bonds in amines can deactivate transition-metal catalysts through coordination. To overcome these limitations, we herein report a practical ligand-regulated metallaphotoredox-catalyzed aminoarylation of ethylene for the direct access to diverse N-(hetero)aryl-substituted arylethylamines from readily available feedstocks, including arenes and (hetero)arylamines. Key to this transformation is the use of diaryl-substituted 1,3-diketone ligands, which effectively modulate the reactivity of the single-electron transfer and proton transfer steps. Our approach not only streamlines the synthesis of structurally diverse N-(hetero)aryl-substituted arylethylamines with excellent functional group tolerance, but also provides a new paradigm for converting ethylene into complex, pharmaceutical relevant molecules. Moreover, the protocol is applicable to propylene, nongaseous alkenes, and 1,3-dienes, underscoring its broad utility in transforming abundant petrochemical feedstocks into value-added products.