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Role of keto-enol tautomerization in the copper-catalyzed hydrogenation of ketones

Jenoff De Vrieze, Joris Thybaut (UGent) and Mark Saeys (UGent)
(2019) ACS CATALYSIS. 9(5). p.3831-3839
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Abstract
Hydrogenation of alkoxy intermediates is often rate-limiting in the hydrogenation of carbonyl groups over copper catalysts. Using first-principles microkinetic simulations with coverage-dependent kinetic parameters, we find that an enol hydrogenation pathway, that is, not passing through alkoxy-intermediates, can become dominant, provided the difference in stability between the adsorbed ketone and enol tautomers is below 30 kjmol(-1). In this scenario, the surface is covered with spectator alkoxides. When water is added, surface alkoxide species can be protonated by surface water or by hydroxyl groups, and oxygen or hydroxyl hydrogenation becomes rate-limiting. We illustrate this change in mechanism for acetol hydrogenation, where the dominant reaction pathway shifts from enol, to aldehyde, and ultimately to ketone hydrogenation with increasing water:acetol feed ratio.
Keywords
hydrogenation, copper, microkinetic modeling, DFT, coverage effects, acetol, ketones, INITIO MOLECULAR-DYNAMICS, FINDING SADDLE-POINTS, ELASTIC BAND METHOD, SELECTIVE HYDROGENATION, HYDROGENOLYSIS, OXIDATION, GLYCEROL, CU, DEHYDROGENATION, MECHANISM

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MLA
De Vrieze, Jenoff, et al. “Role of Keto-Enol Tautomerization in the Copper-Catalyzed Hydrogenation of Ketones.” ACS CATALYSIS, vol. 9, no. 5, 2019, pp. 3831–39, doi:10.1021/acscatal.9b00279.
APA
De Vrieze, J., Thybaut, J., & Saeys, M. (2019). Role of keto-enol tautomerization in the copper-catalyzed hydrogenation of ketones. ACS CATALYSIS, 9(5), 3831–3839. https://doi.org/10.1021/acscatal.9b00279
Chicago author-date
De Vrieze, Jenoff, Joris Thybaut, and Mark Saeys. 2019. “Role of Keto-Enol Tautomerization in the Copper-Catalyzed Hydrogenation of Ketones.” ACS CATALYSIS 9 (5): 3831–39. https://doi.org/10.1021/acscatal.9b00279.
Chicago author-date (all authors)
De Vrieze, Jenoff, Joris Thybaut, and Mark Saeys. 2019. “Role of Keto-Enol Tautomerization in the Copper-Catalyzed Hydrogenation of Ketones.” ACS CATALYSIS 9 (5): 3831–3839. doi:10.1021/acscatal.9b00279.
Vancouver
1.
De Vrieze J, Thybaut J, Saeys M. Role of keto-enol tautomerization in the copper-catalyzed hydrogenation of ketones. ACS CATALYSIS. 2019;9(5):3831–9.
IEEE
[1]
J. De Vrieze, J. Thybaut, and M. Saeys, “Role of keto-enol tautomerization in the copper-catalyzed hydrogenation of ketones,” ACS CATALYSIS, vol. 9, no. 5, pp. 3831–3839, 2019.
@article{8644871,
  abstract     = {{Hydrogenation of alkoxy intermediates is often rate-limiting in the hydrogenation of carbonyl groups over copper catalysts. Using first-principles microkinetic simulations with coverage-dependent kinetic parameters, we find that an enol hydrogenation pathway, that is, not passing through alkoxy-intermediates, can become dominant, provided the difference in stability between the adsorbed ketone and enol tautomers is below 30 kjmol(-1). In this scenario, the surface is covered with spectator alkoxides. When water is added, surface alkoxide species can be protonated by surface water or by hydroxyl groups, and oxygen or hydroxyl hydrogenation becomes rate-limiting. We illustrate this change in mechanism for acetol hydrogenation, where the dominant reaction pathway shifts from enol, to aldehyde, and ultimately to ketone hydrogenation with increasing water:acetol feed ratio.}},
  author       = {{De Vrieze, Jenoff and Thybaut, Joris and Saeys, Mark}},
  issn         = {{2155-5435}},
  journal      = {{ACS CATALYSIS}},
  keywords     = {{hydrogenation,copper,microkinetic modeling,DFT,coverage effects,acetol,ketones,INITIO MOLECULAR-DYNAMICS,FINDING SADDLE-POINTS,ELASTIC BAND METHOD,SELECTIVE HYDROGENATION,HYDROGENOLYSIS,OXIDATION,GLYCEROL,CU,DEHYDROGENATION,MECHANISM}},
  language     = {{eng}},
  number       = {{5}},
  pages        = {{3831--3839}},
  title        = {{Role of keto-enol tautomerization in the copper-catalyzed hydrogenation of ketones}},
  url          = {{http://doi.org/10.1021/acscatal.9b00279}},
  volume       = {{9}},
  year         = {{2019}},
}
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