Computational studies on these systems have typically employed implicit solvation models, overlooking the potential solvent stabilisation of intermediates. Liu and co-workers applied AIMD using the PBE-D3/DZVP level of theory to explore the reaction of a glucosyl trichloroacetimidate donor with different alcohol acceptors in DCM, acetonitrile and methyl tert-butyl ether. Their work revealed that the preferred pathway depends on the solvent and its ability to stabilise the oxocarbenium intermediate. This agrees with the experimental study by Seeberger et al., demonstrating that while the leaving groups do not significantly affect stereoselectivity, the solvent and temperatures can lead to variations in the outcome. Å box, targeting solvent-solute interactions. Finally, subset 3 includes 166 configurations of 28 DCM molecules in a 12.5 Å box, describing bulk solvent-solvent interactions. Subsets 1 and 2 were generated by WTMetaD AL initiated from the RS, minimising potential bias towards a specific mechanism, while subset 3 was collected without any bias. During WTMetaD AL, configurations were labelled with energies and forces computed at the PBE-D3BJ/def2-TZVP level of theory, balancing computational cost and reliable prediction of structures along the reaction paths. This strategy yielded 565 configurations in total (subset 1-3). Validation of the MLIP revealed the highest errors were due to a small number of configurations in the PS region. To address this, six additional gas-phase configurations of distorted PS structures were generated, which improve the accuracy in out-of-equilibrium region in PS (Fig. , details vide infra).