The effect of catalyst restructuring on the polydopamine-supported Pd catalyzed transfer hydrogenation of ethyl 4-nitrobenzoate and the catalytic hydrogenation of (E)-2-methyl-2-butenoic acid is reported. Transmission electron microscopy investigation of different catalyst pre-treatment and reaction conditions revealed high catalytic activity in both reactions unless drastic aggregation of the active metal occurred. In the transfer hydrogenation reaction aggregation was primarily dependent on the H-source used, while in the catalytic hydrogenation additives in combination with the reductive environment led to extensive Pd aggregation and thus decreased catalytic activity. The enantioselective hydrogenation of (E)-2-methyl-2-butenoic acid showed increased enantioselectivity and decreased conversion with increased particle size.
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