Iridium-catalyzed selective N-allylation of hydrazines

A highly chemo- and regioselective iridium-catalyzed allylic amination is described. The reaction of various hydrazones and hydrazides with allylic carbonates proceeds at ambient temperature in the presence of an Ir(COD)Cl]₂/pyridine catalyst, ammonium iodide, and diethylzinc to afford the corresponding N-allylation products in high yields with excellent chemo- and regioselectivities. Only the more nucleophilic nitrogen of a given hydrazine derivative undergoes the C-N bond formation to yield a branched allylic isomer as the exclusive product.