Ni-Catalyzed Regioselective Alkylarylation of Unactivated Alkenes in Amines Enabled by Nitrile and EDA as a Ligand Dyad

We report a Ni-catalyzed vicinal alkylarylation of unactivated alkenes in g,d- and d,e-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 - and -arylamines with C(sp3)-branching at the g- and d-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 a cooperative effect of organic nitriles and electron-deficient alkenes (EDAs) as ligands.