Organocatalytic Nucleophilic Addition of Hydrazones to Imines: Synthesis of Enantioenriched Vicinal Diamines

Abstract

AbstractIn the presence of a catalytic amount of chiral phosphoric acid, nucleophilic addition of N‐monosubstituted hydrazones to N‐Boc imines affords differentially protected vicinal diamines in the form of β‐amino N,N′‐dialkyldiazenes in excellent yields with high chemo‐, diastereo‐, and enantioselectivity. This catalytic asymmetric aza‐Mannich reaction represents the first example in which N‐alkyl hydrazones serve as α‐azo carbanion equivalents to provide vicinal diamines with control of the two contiguous stereocenters. The adducts are readily converted into the monoprotected or free diamines and derivatives thereof.