Monitoring surface processes during heterogeneous asymmetric hydrogenation of ketones on a chirally modified platinum catalyst by operando spectroscopy.

Surface processes occurring at the catalytic chiral surface of a cinchona-modified Pt catalyst during the asymmetric hydrogenation of activated ketones have been monitored for the first time using operando ATR-IR spectroscopy. Fundamental information about this catalytic system could be gained, including the chiral modification process of the catalyst, the surface interaction of reactant ketone with preadsorbed chiral modifier, the role of hydrogen as well as the influence of the product enantiomers in the catalytic cycle. The formation of a diastereomeric transient surface complex between ketone and chiral modifier was found to be related to the ketone consumption. Among the studied activated ketones, a correlation between stereoselection and the strength of the intermolecular hydrogen bond was identified. Dissociated hydrogen from the catalytic surface is found to play a crucial role in the formation of the diastereomeric surface complex.

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