Preparation of Chiral γ-Secondary Amino Alcohols via Ni-Catalyzed Asymmetric Reductive Coupling of 2-Aza-butadiene with Aldehydes.

The first Ni-catalyzed asymmetric reductive coupling of 2-aza-butadiene with aldehydes was achieved to synthesize chiral γ-secondary amino alcohols. This transformation features good enantioselectivity and tolerance to various functional groups, which may serve as a complementary method to previously reported noble-metal-catalyzed protocols. Through competition reaction, 2-aza-butadiene was proved to be a more reactive coupling component than its full-carbon analogue, 1,3-butadiene. Notably, this reaction delivers β-siloxyl imine, an aza-aldol-type product which is difficult to access by conventional methods.