High-effective approach from amino acid esters to chiral amino alcohols over Cu/ZnO/Al(2)O(3) catalyst and its catalytic reaction mechanism

Developing the high-efficient and green synthetic method for chiral amino alcohols is an intriguing target. We have developed the Mg(2+)-doped Cu/ZnO/Al(2)O(3) catalyst for hydrogenation of L-phenylalanine methyl ester to chiral L-phenylalaninol without racemization. The effect of different L-phenylalanine esters on this title reaction was studied, verifying that Cu/ZnO/Al(2)O(3) is an excellent catalyst for the hydrogenation of amino acid esters to chiral amino alcohols. DFT calculation was used to study the adsorption of substrate on the catalyst, and showed that the substrate adsorbs on the surface active sites mainly by amino group (-NH(2)) absorbed on Al(2)O(3), and carbonyl (C=O) and alkoxy (RO-) group oxygen absorbed on the boundary of Cu and Al(2)O(3). This catalytic hydrogenation undergoes the formation of a hemiacetal intermediate and the cleavage of the C–O bond (rate-determining step) by reacting with dissociated H to obtain amino aldehyde and methanol ad-species. The former is further hydrogenated to amino alcohols, and the latter desorbs from the catalyst surface.