Enantio-differentiating hydrogenation of alkyl 3-oxobutanoates over tartaric acid-modified Ni catalyst: Enthalpy-entropy compensation effect as a tool for elucidating mechanistic features

Article abstract of DOI:10.1016/j.mcat.2018.02.023

The enantio-differentiating hydrogenations of a series of alkyl 3-oxobutanoates were carried out at the temperatures ranging from 333 to 393 K over the (R,R)-tartaric acid-modified Ni catalyst prepared from commercially available Ni powder to achieve high enantiomeric excesses of 91-94%. It was demonstrated that the enantio-selectivity was not a simple function of the reaction temperature, being enhanced in the low temperature region to reach a maximum at 363–373 K and then decreased at higher temperatures. Nevertheless, all the differential enthalpies and entropies of activation calculated from the enantiomer ratios in the low and high temperature regions compensated with each other, indicating the same enantio-differentiation mechanism over the entire temperature range. A plausible enantio-differentiation mechanism explaining the effects of hydrogenation temperature on the enantio-selectivity is proposed.