Metal-Controlled, Regioselective, Direct Intermolecular α- or γ-Amination with Azodicarboxylates

A metal-controlled, regioselective intermolecular amination of unsaturated N-acylpyrazoles with azodicarboxylates is described. Under zinc catalysis, the N-acylpyrazole substrates undergo amination at the alpha-position of the N-acylpyrazole moiety. Conversely, with silver as the catalyst, the reaction gave gamma-amination products. Both catalytic protocols provided alternative, convenient, and simple strategies for efficiently and regioselectively accessing structurally unique C -N-bond containing compounds. The synthetic utility of this method was illustrated by a gram-scale experiment and subsequent efficient synthesis of the gamma-amino acid analogue.