Manganese Catalyzed Hydrogenation of Carbamates and Urea Derivatives.

We report the hydrogenation of carbamates and urea derivatives, two of the most challenging carbonyl compounds to be hydrogenated, catalyzed for the first time by a complex of an earth-abundant metal. The hydrogenation reaction of these CO-derived compounds, catalyzed by a manganese pincer complex, yields methanol in addition to amine and alcohol, which makes this methodology a sustainable alternative route for the conversion of CO to methanol, involving a base-metal catalyst. Moreover, the hydrogenation proceeds under mild pressure (20 bar). Our observations support a hydrogenation mechanism involving the Mn-H complex. A plausible catalytic cycle is proposed based on informative mechanistic experiments.