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

• Published in: Chemistry : a European journal 2015-02, Vol.21 (7), p.3097-3107
• Main Authors: Tamura, Masazumi, Tamura, Riku, Takeda, Yasuyuki, Nakagawa, Yoshinao, Tomishige, Keiichi
• Format: Article
• Language: English
• Subjects: Amino acids; amino alcohols; Chemistry; heterogeneous catalysis; Hydrogenation; reaction mechanisms
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.201405769

Hydrogenation of amino acids to amino alcohols is a promising utilization of natural amino acids. We found that MoOx‐modified Rh/SiO2 (Rh–MoOx/SiO2) is an efficient heterogeneous catalyst for the reaction at low temperature (323 K) and the addition of a small amount of MoOx drastically increases the activity and selectivity. Here, we report the catalytic potential of Rh–MoOx/SiO2 and the results of kinetic and spectroscopic studies to elucidate the reaction mechanism of Rh–MoOx/SiO2 catalyzed hydrogenation of amino acids to amino alcohols. Rh–MoOx/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 MoOx modification of Rh metal, which results in high activity, selectivity, and enantioselectivity. Super modifier: Rh–MoOx/SiO2 is a powerful catalyst for hydrogenation of amino acids to amino alcohols (see scheme) and is superior to reported hydrogenation catalysts in terms of activity and substrate scope. For the hydrogenation of carboxylic acids, MoOx species play important roles in the generation of reactive hydride species and adsorption of the substrate.