Reactions of chlorine substituted (E)-2,3-diphenylpropenoic acids over cinchonidine-modified Pd: Enantioselective hydrogenation versus hydrodechlorination
The effect of the chlorine position on the C-Cl bond hydrogenolysis and the enantioselective hydrogenation of Cl substituted (E)-2,3-diphenylpropenoic acid derivatives has been studied over cinchonidine-modified Pd/Al2O3. In contrast to the fast hydrodechlorination of the beta-phenyl-para-Cl substituted acids the Cl on the alpha-phenyl ring was barely hydrogenolized. These observations were interpreted by the different arrangements of the two phenyl rings on the surface, with the alpha- and beta-phenyl rings adsorbed tilted and parallel, respectively. The results confirmed the beneficial effect of the alpha-phenyl-ortho-substituents on the chiral discrimination, thus the 2,3-diphenylpropionic acids substituted by Cl on the alpha-phenyl ring could be prepared in good yields and optical purities. The conclusions were used for the rational design of an acid, i.e. (E)-2-(2-methoxyphenyl)-3-(3,4-difluorophenyl)propenoic acid, which afforded the best optical purity (ee up to 95% at 295 K) described until now in this heterogeneous system. (C) 2010 Elsevier B.V. All rights reserved.
Up to 96% Enantioselectivities in the Hydrogenation of Fluorine Substituted (E)-2,3-Diphenylpropenoic Acids over Cinchonidine-Modified Palladium Catalyst
High enantioselectivities, up to 96%, were obtained in the hydrogenation of some disubstituted derivatives, unprecedented in the hydrogenation of prochiral unsaturated carboxylicacidsovermodified heterogeneous catalyst. The best optical purities were reached in the hydrogenation of derivates bearing a para-substituent on the β phenyl and an ortho-substituent on the α phenyl ring, respectively. The
Asymmetric transfer hydrogenation of 2,3-diphenylpropenoic acids over heterogeneous palladium catalysts modified by cinchona alkaloids
作者:György Szőllősi、Vivien Erzsébet Resch、Vanessza Judit Kolcsár
DOI:10.1016/j.jcat.2024.115290
日期:2024.1
supported palladium catalysts modified by dihydrocinchonidine carried out in ordinary laboratory glassware using easily available, cheap hydrogen donor, potassium formate. High conversions and good enantioselectivities were obtained in transfer hydrogenations of various acids substituted on phenyl rings. Results obtained with various acid derivatives and with few cinchona alkaloid modifiers indicated that