Directed Nickel-Catalyzed Diastereoselective Reductive Difunctionalization of Alkenyl Amines

We report herein an intermolecular syn-arylalkylation and alkenylalkylation of alkenyl amines with two different organohalides (iodides and bromides) using Ni(II) catalyst. The cleavable bidentate quinolinamide is utilized after extensive directing group screening to enable olefin difunctionalization with high levels of regio-, chemo-, and diastereocontrol. This general and practical protocol is compatible with alpha - or beta-substituted terminal alkenes and internal alkenes, providing rapid access to branched aliphatic amines bearing two skipped and vicinal stereocenters with high diastereoselectivities that would otherwise be difficult to synthesize.