Ni-Catalyzed Regioselective Alkylarylation of Unactivated Alkenes in Amines Enabled by Cooperative Ligand Effects of Nitriles and Electron-Deficient Alkenes

We report a Ni-catalyzed vicinal alkylarylation of unactivated alkenes in γ,δ- and δ,ε-alkenylamines with aryl halides and alkylzinc reagents. The reaction is enabled by amine coordination and can use all primary, secondary, and tertiary amines. The reaction constructs two new C(sp³)–C(sp³) and C(sp³)–C(sp²) bonds and produces δ- and ε-arylamines with C(sp³)-branching at the γ- and δ-positions. A variety of aryl and heteroaryl iodides and both the primary and secondary alkylzinc reagents can be used as coupling carbon sources. Mechanistic studies suggest that the reaction is enabled by the cooperative effect of organic nitriles and electron-deficient alkenes (EDAs) as ligands.