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Autocatalytic role of molecular hydrogen in copper-catalyzed transfer hydrogenation of ketones

Jenoff De Vrieze, César A. Urbina-Blanco (UGent) , Joris Thybaut (UGent) and Mark Saeys (UGent)
(2019) ACS CATALYSIS. 9(9). p.8073-8082
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Organization
Abstract
Catalytic transfer hydrogenation of ketones and aldehydes is generally accepted to follow a dehydrogenation-hydrogenation mechanism on copper, which makes the increased hydrogenation rate and selectivity rather puzzling. Using first-principles microkinetics on a Cu(111) surface, we show that, rather than a dehydrogenation-hydrogenation mechanism, there is also direct proton transfer between the sacrificial alcohol and the reacting ketone. The ketone is hydrogenated to a stable alkoxy intermediate using surface hydrogen. This alkoxy intermediate is subsequently hydrogenated to the alcohol product via direct proton transfer from the sacrificial alcohol, also forming a sacrificial alkoxy intermediate. To close the catalytic cycle, the sacrificial alkoxy species dehydrogenates, forming its corresponding ketone. We also observed a surprising catalytic effect of molecular hydrogen, which can be explained by the rate-controlling step in transfer hydrogenation: the direct hydrogenation of the ketone to its alkoxy intermediate by surface hydrogen. Under all realistic reaction conditions, this step has the highest degree of rate control.
Keywords
transfer hydrogenation, copper, microkinetic modeling, DFT, ketones, FINDING SADDLE-POINTS, FURFURYL ALCOHOL, CARBONYL-COMPOUNDS, ACTIVE-SITES, CU, DEHYDROGENATION, OXIDATION, COVERAGE, METHANOL, 2-METHYLFURAN

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MLA
De Vrieze, Jenoff, et al. “Autocatalytic Role of Molecular Hydrogen in Copper-Catalyzed Transfer Hydrogenation of Ketones.” ACS CATALYSIS, vol. 9, no. 9, 2019, pp. 8073–82, doi:10.1021/acscatal.9b01759.
APA
De Vrieze, J., Urbina-Blanco, C. A., Thybaut, J., & Saeys, M. (2019). Autocatalytic role of molecular hydrogen in copper-catalyzed transfer hydrogenation of ketones. ACS CATALYSIS, 9(9), 8073–8082. https://doi.org/10.1021/acscatal.9b01759
Chicago author-date
De Vrieze, Jenoff, César A. Urbina-Blanco, Joris Thybaut, and Mark Saeys. 2019. “Autocatalytic Role of Molecular Hydrogen in Copper-Catalyzed Transfer Hydrogenation of Ketones.” ACS CATALYSIS 9 (9): 8073–82. https://doi.org/10.1021/acscatal.9b01759.
Chicago author-date (all authors)
De Vrieze, Jenoff, César A. Urbina-Blanco, Joris Thybaut, and Mark Saeys. 2019. “Autocatalytic Role of Molecular Hydrogen in Copper-Catalyzed Transfer Hydrogenation of Ketones.” ACS CATALYSIS 9 (9): 8073–8082. doi:10.1021/acscatal.9b01759.
Vancouver
1.
De Vrieze J, Urbina-Blanco CA, Thybaut J, Saeys M. Autocatalytic role of molecular hydrogen in copper-catalyzed transfer hydrogenation of ketones. ACS CATALYSIS. 2019;9(9):8073–82.
IEEE
[1]
J. De Vrieze, C. A. Urbina-Blanco, J. Thybaut, and M. Saeys, “Autocatalytic role of molecular hydrogen in copper-catalyzed transfer hydrogenation of ketones,” ACS CATALYSIS, vol. 9, no. 9, pp. 8073–8082, 2019.
@article{8624928,
  abstract     = {{Catalytic transfer hydrogenation of ketones and aldehydes is generally accepted to follow a dehydrogenation-hydrogenation mechanism on copper, which makes the increased hydrogenation rate and selectivity rather puzzling. Using first-principles microkinetics on a Cu(111) surface, we show that, rather than a dehydrogenation-hydrogenation mechanism, there is also direct proton transfer between the sacrificial alcohol and the reacting ketone. The ketone is hydrogenated to a stable alkoxy intermediate using surface hydrogen. This alkoxy intermediate is subsequently hydrogenated to the alcohol product via direct proton transfer from the sacrificial alcohol, also forming a sacrificial alkoxy intermediate. To close the catalytic cycle, the sacrificial alkoxy species dehydrogenates, forming its corresponding ketone. We also observed a surprising catalytic effect of molecular hydrogen, which can be explained by the rate-controlling step in transfer hydrogenation: the direct hydrogenation of the ketone to its alkoxy intermediate by surface hydrogen. Under all realistic reaction conditions, this step has the highest degree of rate control.}},
  author       = {{De Vrieze, Jenoff and Urbina-Blanco, César A. and Thybaut, Joris and Saeys, Mark}},
  issn         = {{2155-5435}},
  journal      = {{ACS CATALYSIS}},
  keywords     = {{transfer hydrogenation,copper,microkinetic modeling,DFT,ketones,FINDING SADDLE-POINTS,FURFURYL ALCOHOL,CARBONYL-COMPOUNDS,ACTIVE-SITES,CU,DEHYDROGENATION,OXIDATION,COVERAGE,METHANOL,2-METHYLFURAN}},
  language     = {{eng}},
  number       = {{9}},
  pages        = {{8073--8082}},
  title        = {{Autocatalytic role of molecular hydrogen in copper-catalyzed transfer hydrogenation of ketones}},
  url          = {{http://doi.org/10.1021/acscatal.9b01759}},
  volume       = {{9}},
  year         = {{2019}},
}
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