Ni-Catalyzed Regioselective and Site-divergent Reductive Arylalkylations of Allylic Amines

Catalytic methods allow for regioselective and site-divergent transformations for rapid construction of different complex architectures from identical and readily-available starting materials by switching the least parameters are among the most ideal catalytic protocols. However, the associated challenge to precisely control both regioselectivity and site-diversity renders this strategy appealing yet challenging. Herein, a Ni-catalyzed cross-electrophile regioselective and site-divergent 1,2- and 1,3-arylalkylations of allylic amines have been developed. This Ni-catalyzed reductive three-component protocol enables 1,2-arylalkylation and 1,3-arylalkylations of allylic amines with aryl halides and alkyl halides with excellent chemo-, regio- and site-selectivity, representing the first example of controlled migratory difunctionalization of alkenes under reductive conditions. A wide range of sterically and electronically differentiated terminal and internal unactivated allylic amines, aryl halides and alkyl precursors were tolerated, providing a straightforward and efficient access to diverse C(sp3)-rich branched aliphatic amines from identical starting materials.