Abstract
Catalytic methods by switching the least parameters for regioselective and site-divergent transformations to construct different architectures from identical and readily available starting materials 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, Ni-catalyzed cross-electrophile regioselective and site-divergent 1,2- and 1,3-arylalkylations of N-acyl allylic amines have been developed. This Ni-catalyzed reductive three-component protocol enables 1,2-arylalkylation and 1,3-arylalkylation 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 terminal and internal unactivated allylic amines, aryl halides and alkyl precursors were tolerated, providing straightforward and efficient access to diverse C(sp(3))-rich branched aliphatic amines from identical starting materials.