Abstract and subjects
The mechanism of ketones homogeneous hydrogenation with t-BuOK in tert-butanol is currently portrayed as the one proceeding via a six-membered [2 + 2 + 2] cyclic transition state involving the H-2 molecule, the base, and a ketone. However, the concerted nature of the reaction is inconsistent with a number of experimental observations. Here we reanalyze available experimental data and revise the mechanism of this paradigmatic reaction based on the static and dynamic density functional theory (DFT) calculations in solution phase. In contrast to the gas-phase profile where the overall reaction occurs in two elementary steps, there are three consecutive steps in solution: cleavage of the H-H bond in basic tert-butanol to afford potassium hydride, addition of potassium hydride across the C = O bond of a ketone through the rate-determining transition state, and rapid product formation through K/H exchange. Potassium hydride is therefore an important intermediate of the catalytic process. The free energy profile for the prophetic ester homogeneous hydrogenation with t-BuOK in tert-butanol is also computed herein. The reaction seems to be kinetically possible, but slightly harsher conditions need to be applied, consistent with rate-determining nature of the potassium hydride addition.