ja9b05591_si_001.pdf (2.13 MB)
Manganese Catalyzed Hydrogenation of Carbamates and Urea Derivatives
journal contribution
posted on 2019-08-07, 14:40 authored by Uttam
Kumar Das, Amit Kumar, Yehoshoa Ben-David, Mark A. Iron, David MilsteinWe
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.