American Chemical Society
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Manganese Catalyzed Hydrogenation of Carbamates and Urea Derivatives

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journal contribution
posted on 2019-08-07, 14:40 authored by Uttam Kumar Das, Amit Kumar, Yehoshoa Ben-David, Mark A. Iron, David Milstein
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 CO2-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 CO2 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.