We note that the 2-naphthol and the thiocyanating reagent have not been considered from the starting point of the calculation, i.e., from Intrm1, as the enantioselective step in the complete cycle is the formation of TSwyn2A. This reduces the computational cost without hampering the reliability. After the formation of Intrm2, the 2-naphthol(Ad) additive and N- in the SI). The energy differences between the enantio-controlling TSs are somewhat overestimated by the DFT calculations. This is not an uncommon situation in quantum mechanical investigations of catalysis, as has been pointed out earlier, for instance, by Houk and coworkers. 41