Theoretical study on the mechanism of hydromethoxylation catalyzed by palladium(II) complex

Palladium (II) coordination complexes catalyze the reaction of alcohols with ketones to yield ethers. During the catalytic cycle, the alcohol adds selectively to the B-carbon (anti-Markovnikov). In this work, mechanism and kinetics for the reaction of methanol with methyl vinyl ketone (MVK), being catalyzed by Pd, has been theoretically investigated in detail. Using quantum mechanical approach, different probabilities were investigated and ultimately a model was presented in which an enol form is produced in the rate determining step and in continuation is converted into keto form. Considering the solvent effects, the activation energy and the change in Gibbs free energy for the formation of the activated complex for the rate determining step were calculated, which are in good agreement with the experimental value. The evaluation of keto-enol equilibrium constant also showed that the keto form is much more stable than the enol form.