Zinc-Catalyzed Asymmetric Synthesis of anti-1,2-Nitroamines

Significance

The asymmetric aza-Henry reaction is a new application of the dinuclear metal catalyst 3 developed by the Trost group. Although Shibasaki has carried out seminal studies on the addition of nitroenolates to C=N groups, the method expands the scope of the imine reacting partner to encompass a range of α-substituents to the imine, as well as the nature of the nitrogen protecting group. Of particular synthetic interest are α,β-unsaturated adducts like 9 and 10. The α-nitro­amines 4-10 obtained are useful precursors to chiral 1,2-diamines by reduction, or to α-amino acids by oxidative cleavage.