The regioselective hydroamination of unactivated alkenes is a long-standing challenge in organic synthesis. Herein, we report a NiH-catalyzed proximal-selective hydroamination of unactivated alkenes with 8-aminoquinoline (AQ) as a bidentate auxiliary and anthranils as aminating reagents. A wide range of primary aryl amines bearing an ortho-carbonyl group were installed in both terminal and internal unactivated alkenes, delivering a variety of valuable β- and γ-amino acid building blocks, respectively, with excellent regiocontrol. The utility of this transformation was further demonstrated by the conversion of the multifunctionalized aryl amines into useful N-heterocycles.