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Catalysts 2017, 7(9), 264; doi:10.3390/catal7090264

Mechanistic Insight into the 2° Alcohol Oxidation Mediated by an Efficient CuI/L-Proline-TEMPO Catalyst—A Density Functional Theory Study

1
College of Chemical Engineering, Inner Mongolia University of Technology, Inner Mongolia Key Laboratory of Theoretical and Computational Chemistry Simulation, Hohhot 010051, China
2
High Performance Computing Center of Jilin University, Changchun 130022, China
*
Authors to whom correspondence should be addressed.
Received: 10 August 2017 / Revised: 31 August 2017 / Accepted: 31 August 2017 / Published: 5 September 2017
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Abstract

Density functional theory (DFT) calculations have been performed to investigate the 2° alcohol oxidation to acetophenone catalyzed by the CuI/L-Proline-2,2,6,6- tetramethylpiperidinyloxy (TEMPO) catalyst system. Seven possible pathways (paths A→F) are presented. Our calculations show that two pathways (path A and path B) are the potential mechanisms. Furthermore, by comparing with experimental observation, it is found that path A—in which substrate alcohol provides the proton to OtBu to produce HOtBu followed by the oxidation of substrate directly to product acetophenone by O2—is favored in the absence of TEMPO. Correspondingly, path B is likely to be favored when TEMPO is involved. In path B, the O–O bond cleavage of CuI–OOH to CuII–OH species occurs, followed by acetophenone formation assisted by ligand (L)2ˉ. It is also found that the cooperation of ligand (L)2ˉ and TEMPO plays an important role in assisting the formation of the product acetophenone in path B. View Full-Text
Keywords: alcohol oxidation; reaction mechanism; density functional theory; aerobic oxidation; energetic span model alcohol oxidation; reaction mechanism; density functional theory; aerobic oxidation; energetic span model
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MDPI and ACS Style

Li, S.; Cheng, L.; Wu, Q.; Zhang, Q.; Yang, J.; Liu, J. Mechanistic Insight into the 2° Alcohol Oxidation Mediated by an Efficient CuI/L-Proline-TEMPO Catalyst—A Density Functional Theory Study. Catalysts 2017, 7, 264.

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