Manganese Catalyzed Hydrogenation of Carbamates and Urea Derivatives

Uttam Kumar Das; Amit Kumar; Yehoshoa Ben-David; Mark A. Iron; David Milstein

doi:10.1021/jacs.9b05591

Manganese Catalyzed Hydrogenation of Carbamates and Urea Derivatives

Uttam Kumar Das, Amit Kumar, Yehoshoa Ben-David, Mark A. Iron, David Milstein^*

^*Corresponding author for this work

Department of Chemical Research Support

Research output: Contribution to journal › Letter › peer-review

110 Citations (Scopus)

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Abstract

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.

Original language	English
Pages (from-to)	12962-12966
Number of pages	5
Journal	Journal of the American Chemical Society
Volume	141
Issue number	33
Early online date	31 Jul 2019
DOIs	https://doi.org/10.1021/jacs.9b05591
Publication status	Published - 21 Aug 2019

Funding

This research was supported by the European Research Council (ERC AdG 692775), and by the Israel Science Foundation. U.K.D. is thankful to Gov’t. of India for the DST SERB Overseas Postdoctoral Fellowship.

All Science Journal Classification (ASJC) codes

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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title = "Manganese Catalyzed Hydrogenation of Carbamates and Urea Derivatives",

abstract = "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.",

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AU - Das, Uttam Kumar

AU - Kumar, Amit

AU - Ben-David, Yehoshoa

AU - Iron, Mark A.

AU - Milstein, David

PY - 2019/8/21

Y1 - 2019/8/21

N2 - 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.

AB - 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.

UR - https://www.scopus.com/pages/publications/85070967852

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DO - 10.1021/jacs.9b05591

M3 - Letter

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EP - 12966

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 33

ER -

Manganese Catalyzed Hydrogenation of Carbamates and Urea Derivatives

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