General Ir-Catalyzed N-H Insertions of Diazomalonates into Aliphatic and Aromatic Amines

A general N-H insertion reactivity of acceptor-acceptor diazo malonate reagents is reported using [Ir-(cod)-Cl](2) as catalyst. A large range of amines, primary and secondary, aliphatic and aromatic, is possible. Mild temperatures, perfect substrate/reactant stoichiometry, and good functional group compatibility render the process particularly attractive for the (late-stage) functionalization of amines.