Air Stable Iridium Catalysts for Direct Reductive Amination of Ketones

Half-sandwich iridium complexes bearing bidentate urea-phosphorus ligands were found to catalyze the direct reductive amination of aromatic and aliphatic ketones under mild conditions at 0.5 mol % loading with high selectivity towards primary amines. One was be active in both Leuckart–Wallach (NH4CO2H) type reaction as well hydrogenative (H2/NH4AcO) amination. The protocol ammonium formate does not require an inert atmosphere, dry solvents, additives contrast previous reports takes place hexafluoroisopropanol (HFIP) instead methanol. Applying NH4CO2D or D2 resulted a degree deuterium incorporation into amine α-position.