The development of new strategies for the preparation of chiral amines is an important objective in organic synthesis. In this Synpacts , we summarize our approach for catalytically accessing nucleophilic aminoalkyl metal species from 2-azadienes, and its application in generating a number of important but elusive chiral amine scaffolds. Reductive couplings with ketones and imines afford 1,2-amino tertiary alcohols and 1,2-diamines, respectively, whereas fluoroarylations of gem -difluoro-2-azadienes deliver α-trifluoromethylated benzylic amines.