Insight into the Mechanism of Hydrogenation of Amino Acids to Amino Alcohols Catalyzed by a Heterogeneous MoOx‐Modified Rh Catalyst

Hydrogenation of amino acids to amino alcohols is a promising utilization of natural amino acids. We found that MoO_x‐modified Rh/SiO₂ (Rh–MoO_x/SiO₂) is an efficient heterogeneous catalyst for the reaction at low temperature (323 K) and the addition of a small amount of MoO_x drastically increases the activity and selectivity. Here, we report the catalytic potential of Rh–MoO_x/SiO₂ and the results of kinetic and spectroscopic studies to elucidate the reaction mechanism of Rh–MoO_x/SiO₂ catalyzed hydrogenation of amino acids to amino alcohols. Rh–MoO_x/SiO₂ is superior to previously reported catalysts in terms of activity and substrate scope. This reaction proceeds by direct formation of an aldehyde intermediate from the carboxylic acid moiety, which is different from the reported reaction mechanism. This mechanism can be attributed to the reactive hydride species and substrate adsorption caused by MoO_x modification of Rh metal, which results in high activity, selectivity, and enantioselectivity.