Inaccessibility of beta-hydride elimination from -OH functional groups in Wacker-type oxidation

Journal of the American Chemical Society
John A KeithWilliam A Goddard

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 (beta-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 beta atom is not an alkyl group.

References

Mar 3, 2005·Journal of the American Chemical Society·Candace N Cornell, Matthew S Sigman

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Citations

Aug 31, 2007·Chemical Communications : Chem Comm·Cong LiuRoss A Widenhoefer
Jun 24, 2010·Chemistry : a European Journal·Aleix Comas-VivesGregori Ujaque
Aug 27, 2014·Chemistry : a European Journal·Ricardo A AngnesCarlos Roque D Correia
Nov 5, 2014·Angewandte Chemie·Jia Jia DongBen L Feringa
Oct 17, 2009·Angewandte Chemie·John A Keith, Patrick M Henry
Jun 7, 2019·Chemistry : a European Journal·Michiel Janssen, Dirk E De Vos
Dec 18, 2010·Dalton Transactions : an International Journal of Inorganic Chemistry·Bing WuXuefeng Fu
Mar 16, 2013·Chemistry : a European Journal·Venkataramana ImandiNisanth N Nair
Feb 3, 2021·Organic Letters·Bao-Yin ZhaoYong-Qiang Wang
Jan 17, 2008·The Journal of Physical Chemistry. a·Kimberly ChenowethWilliam A Goddard
Apr 17, 2010·Journal of the American Chemical Society·Ming-Kui ZhuTeck-Peng Loh
Aug 7, 2010·Journal of the American Chemical Society·Brian J AndersonMatthew S Sigman
Dec 24, 2010·Journal of the American Chemical Society·Carl A LaskowskiThomas R Cundari
Aug 28, 2020·Journal of the American Chemical Society·Xing-Wang HanMaurice Brookhart
Apr 20, 2018·Inorganic Chemistry·Felix Schroeter, Thomas Strassner
Apr 23, 2015·The Journal of Physical Chemistry. B·Venkataramana Imandi, Nisanth N Nair
Nov 28, 2017·The Journal of Organic Chemistry·Rauful Alam, Gary A Molander
Sep 21, 2007·Journal of the American Chemical Society·John A KeithWilliam A Goddard
Mar 14, 2007·Journal of the American Chemical Society·Erik ZuidemaPiet W N M van Leeuwen

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