Aldol Condensation of Cyclopentanone on Hydrophobized MgO. Promotional Role of Water and Changes in the Rate-Limiting Step upon Organosilane Functionalization

Aldol condensation is a key C—C coupling reaction for upgrading of biomass-derived oxygenates to fuels and chemicals. Here, we investigate the effects of added water on the condensation of cyclopentanone (CPO) on hydrophobized MgO catalysts. We have found that the role of water strongly depends on the degree of hydrophobic functionalization of the MgO surface. That is, on a nonfunctionalized (hydrophilic) high-surface-area MgO catalyst, the rate decreases with the addition of water, mostly due to active site blockage. By contrast, on MgO hydrophobized via silylation with octadecyltrichlorosilane (OTS), the rate actually increases with added water. A concomitant change in kinetics is observed from the pristine (hydrophilic) MgO to the hydrophobized sample. Specifically, on the hydrophilic sample, the reaction is first-order, as expected if the rate-limiting step is the formation of an enolate intermediate via α-H abstraction at a basic site, as widely reported in previous literature. By contrast, on the hy...