A Theoretical Study of Ene Reactions in Solution: A Solution-Phase Translational Entropy Model.

Abstract

Several density functional theory (DFT) methods, such as CAM-B3LYP, M06, ωB97x, and ωB97xD, are used to characterize a range of ene reactions. The Gibbs free energy, activation enthalpy, and entropy are calculated with both the gas- and solution-phase translational entropy; the results obtained from the solution-phase translational entropies are quite close to the experimental measurements, whereas the gas-phase translational entropies do not perform well. For ene reactions between the enophile propanedioic acid (2-oxo-1,3-dimethyl ester) and π donors, the two-solvent-involved explicit+implicit model can be employed to obtain accurate activation entropies and free-energy barriers, because the interaction between the carbonyl oxygen atom and the solvent in the transition state is strengthened with the formation of C-C and O-H bonds. In contrast, an implicit solvent model is adequate to calculate activation entropies and free-energy barriers for the corresponding reactions of the enophile 4-phenyl-1,2,4-triazoline-3,5-dione.