The statement “Based on previous literature (J. Phys. Chem. A 2018, 122, 1392–1399), the contribution of entropy to the reaction is minimal; therefore, it suffices to calculate the free energy using dispersion-corrected DFT functionals” raises some concerns. Firstly, I do not fully agree with the generalization that entropy plays a minimal role in this reaction. Numerous experimental and theoretical studies have highlighted significant differences between potential energy surfaces (PES) and free energy surfaces (FES), especially in large systems (with or without limitd conformational flexibility). Even if part of the system is rigid, the overall system might adopt various conformers with distinct energies when considering the substrate. Secondly, the reasoning that dispersion-corrected DFT functionals alone can account for free energy contributions is unclear—this relates to the level of theory used for energy calculations, not the inclusion of entropic or enthalpic contributions that can be renderd by statistical samplings. Moreover, if entropy is indeed negligible, it is not clear why the authors use (approximate) free energies to correlate NPA charges in intermediate 6, instead of just potential energies.