Cinchona-modified platinum catalysts: from ligand acceleration to technical processes

This Account records work carried out in our laboratories during the last 2 decades in the field of enantioselective heterogeneous hydrogenation. Of particular interest was Orito's catalytic system, platinum catalysts modified with cinchona alkaloids for the hydrogenation of activated ketones. Described are the development of the optimal platinum catalyst and modifier and the expansion of the scope of the catalyst. Kinetic studies aimed at understanding the mode of action of the catalyst revealed that the cinchona modifier not only renders the catalyst enantioselective but strongly accelerates the hydrogenation. This was the first case of ligand acceleration with a heterogeneous catalytic system. Finally, a number of industrial processes are summarized with the enantioselective hydrogenation of various alpha-keto esters as a key step.