Table 2. Basis set superposition errors for R=Ph.

The ten year old Houk-List model, for rationalising the origin of stereoselectivity in the organocatalysed intermolecular aldol addition, is revisited using a variety of computational techniques which have been introduced or improved since the original study. Even for such a relatively small system, the role of dispersion interactions is shown to be crucial, along with the use of basis sets where the superposition errors are low. Understanding the non covalent interactions (NCI) at play is highlighted as essential for the design of new synthetic routes and alternative reactants. An NCI analysis of the transition states enables the identification of non-covalent interactions that determine the reaction outcome, confirming the role of the electrostatic NCHᵟ+∙∙∙Oᵟ- interactions and highlighting new geometric schemes based on dispersion. Alternative mechanisms, such as proton-relays involving a water molecule or the Hajos-Parrish alternative, are shown to be higher in energy. The Amsterdam manifesto, which espouses the principle that scientific data should be citable, is followed here by using interactive data tables assembled via calls to the data DOI (digital-object-identifiers) held on a digital repository.