The reaction is initiated by formation of a reactant complex with a hydrogen bond between the carbamate hydrogen and imidate nitrogen. The complex undergoes a proton transfer via TS1, to form an intermediate ion pair (INT1). This ion pair can change conformation to a new intermediate ion pair (INT2), where the TCA-group is rotated so that one of the protonated imine hydrogens forms a hydrogen bond to the oxygen at C-2 and the carbamate surrounds the TCA-donor. Then the ion pair passes through TS2, the transition state for leaving group departure, which yields the oxocarbenium-like ionpair INT3. INT3 has the deprotonated carbamate nitrogen in the right position for attack of the anomeric carbon to give the β-N -glucoside product via TS3. It is seen from the reaction coordinate, that INT1 is higher in energy than TS1, which is not physically possible. However, looking at Table S.4 (Section 6.1), it is evident that the pure DFT energy is higher for the transition state, but when including zero-point vibrational energies and thermodynamic contributions, it becomes lower. This is most likely due to approximations made when calculating the zero-point vibrational and thermodynamic contributions. Hence, TS1 and INT1 must be very similar in energy, which is also illustrated by their almost identical structure, in line with the Hammond postulate. Multiple attempts to locate a more S N 2-like pathway failed, and we therefore suggest that the reaction mainly proceeds via this more S N 1-like pathway. This is also in line with previous observations by Pinna et al. In Figure the transition states with displacement vectors, which show the motion of the molecule during the transition state, are displayed. It is seen that during the proton transfer (TS1), the motion is localized to the proton, whereas for TS2, the anomeric carbon and the endocyclic oxygen move away from the leaving group to form the oxocarbenium-ion like intermediate, while the leaving group is departing. In TS3 the vectors illustrate the movement of the anomeric carbon and carbamate nitrogen towards each other. This is in accordance with an S N 1-like reaction initiated by a proton transfer.