Premodification of Pt/γAl2O3 with cinchonidine for the enantioselective hydrogenation of ethyl pyruvate:: effect of premodification conditions on reaction rate and enantioselection

The premodification of a 5 wt% Pt=gamma-Al2O3 catalyst with cinchonidine (0.01 and 0.2 g g(catalyst)(-1)) is described and discussed. Premodification is carried out by treating the catalyst with a solution of cinchonidine followed by solvent removal. Catalysts premodified in this way give the same ee and initial rate of reaction for the enantioselective hydrogenation of ethyl pyruvate as those using the standard in situ modi. cation procedure. Investigations of different solvents for premodification and reaction ( dichloromethane, ethanol) show that it is the solvent used for the reaction that controls the observed enantioselection. Premodified catalysts also display the initial transient behavior typically observed with in situ modified catalysts in which the ee increases with conversion in the early part of the reaction. Premodified catalysts show an enhanced rate of reaction when ethanol is used as the reaction solvent compared with in situ modified catalysts under the same conditions. Premodification using aerobic conditions gives the best results and premodified catalysts can be stored prior to use for up to a week without loss of catalytic performance.