We introduce a new reagent class, 2-azatrienes, as a platform for catalytic enantioselective synthesis of allylic amines. Herein, we demonstrate their promise by diasteredivergent and enantioselective synthesis of syn - and anti -1,2-diamines by Cu-bis(phosphine)-catalyzed reductive couplings with imines. With Ph-BPE, anti -diamines are obtained, and with the rarely utilized t-Bu-BDPP, syn -diamines are generated.