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Inaccessibility of β-Hydride Elimination from −OH Functional Groups in Wacker-Type Oxidation

Keith, John A. and Oxgaard, Jonas and Goddard, William A., III (2006) Inaccessibility of β-Hydride Elimination from −OH Functional Groups in Wacker-Type Oxidation. Journal of the American Chemical Society, 128 (10). pp. 3132-3133. ISSN 0002-7863. https://resolver.caltech.edu/CaltechAUTHORS:20170427-082648149

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Abstract

Quantum mechanics calculations (B3LYP and MPW1K density functional theory) on mechanisms relevant to the Wacker process for dehydrogenation of alcohol to ketone show that the commonly accepted mechanism for product formation (β-hydride elimination (BHE) leading to Pd−H formation) is not energetically feasible (36.2 kcal/mol). An alterative pathway involving a five-bodied reductive elimination (RE) leads to an activation enthalpy of 18.8 kcal/mol, which is just half that of the BHE from the −OH group usually assumed for the Wacker process. We find that a water molecule catalyzes both processes, reducing the barrier to 17.2 for RE and 25.0 for BHE, but will not change the relative ordering of the two mechanisms. This suggests that assumptions of BHE mechanisms should be reexamined for cases in which the β atom is not an alkyl group.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ja0533139DOIArticle
http://pubs.acs.org/doi/suppl/10.1021/ja0533139PublisherSupporting Information
ORCID:
AuthorORCID
Keith, John A.0000-0002-6583-6322
Goddard, William A., III0000-0003-0097-5716
Additional Information:© 2006 American Chemical Society. Received May 20, 2005; Revised Manuscript Received November 1, 2005. Publication Date (Web): February 18, 2006. J.A.K. expresses his gratitude to G. O. Spessard, R. J. Nielsen, and J. S. Su for helpful discussions and insight. This research was partially supported by the Chevron-Texaco Energy Research and Technology Company.
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Chevron-Texaco Energy Research and Technology Co.UNSPECIFIED
Issue or Number:10
Record Number:CaltechAUTHORS:20170427-082648149
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20170427-082648149
Official Citation:Inaccessibility of β-Hydride Elimination from −OH Functional Groups in Wacker-Type Oxidation John A. Keith, Jonas Oxgaard, and William A. Goddard, III Journal of the American Chemical Society 2006 128 (10), 3132-3133 DOI: 10.1021/ja0533139
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:76980
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:27 Apr 2017 16:37
Last Modified:27 Feb 2020 23:38

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