High-effective approach from amino acid esters to chiral amino alcohols over Cu/ZnO/Al2O3 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/Al2O3 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/Al2O3 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 (-NH2) absorbed on Al2O3, and carbonyl (C=O) and alkoxy (RO-) group oxygen absorbed on the boundary of Cu and Al2O3. 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.
Research Institute of Applied Catalysis, School of Chemical and Environmental Engineering, Shanghai Institute of Technology, Shanghai 201418, China.
Shuangshuang
S
Zhang
Research Institute of Applied Catalysis, School of Chemical and Environmental Engineering, Shanghai Institute of Technology, Shanghai 201418, China.
Jun
J
Yu
Research Institute of Applied Catalysis, School of Chemical and Environmental Engineering, Shanghai Institute of Technology, Shanghai 201418, China.
Huiying
H
Li
Research Institute of Applied Catalysis, School of Chemical and Environmental Engineering, Shanghai Institute of Technology, Shanghai 201418, China.
Dongsen
D
Mao
Research Institute of Applied Catalysis, School of Chemical and Environmental Engineering, Shanghai Institute of Technology, Shanghai 201418, China.|Key Laboratory for Advanced Materials and Research Institute of Industrial catalysis, East China University of Science and Technology, Shanghai 200237, China.
Guanzhong
G
Lu
D000327:Adsorption; D000537:Aluminum Oxide / Q000737:chemistry*; D000596:Amino Acids / Q000737:chemistry*; D000605:Amino Alcohols / Q000138:chemical synthesis / Q000737:chemistry*; D002384:Catalysis; D060326:Chemistry Techniques, Synthetic / Q000379:methods; D003300:Copper / Q000737:chemistry*; D004952:Esters / Q000737:chemistry; D006865:Hydrogenation; D008956:Models, Chemical; D008958:Models, Molecular; D008968:Molecular Conformation; D015394:Molecular Structure; D013237:Stereoisomerism; D015034:Zinc Oxide / Q000737:chemistry*
D000596:Amino Acids; D000605:Amino Alcohols; D004952:Esters; D003300:Copper; D000537:Aluminum Oxide; D015034:Zinc Oxide