Mechanistic Investigation of Molybdate‐Catalysed Transfer Hydrodeoxygenation

The molybdate‐catalysed transfer hydrodeoxygenation (HDO) of benzyl alcohol to toluene driven by oxidation of the solvent isopropyl alcohol to acetone has been investigated by using a combination of experimental and computational methods. A Hammett study that compared the relative rates for the transfer HDO of five para‐substituted benzylic alcohols was carried out. Density‐functional theory (DFT) calculations suggest a transition state with significant loss of aromaticity contributes to the lack of linearity observed in the Hammett study. The transfer HDO could also be carried out in neat PhCH₂OH at 175 °C. Under these conditions, PhCH₂OH underwent disproportionation to yield benzaldehyde, toluene, and significant amounts of bibenzyl. Isotopic‐labelling experiments (using PhCH₂OD and PhCD₂OH) showed that incorporation of deuterium into the resultant toluene originated from the α position of benzyl alcohol, which is in line with the mechanism suggested by the DFT study.