Abstract In this study, a theoretical analysis of the torquoselectivity in a set of unusual ring‐opening reactions (R1‐R5) is presented. To describe the mechanism of the reactions, a recent methodology has been used to estimate the electrophilicities of the natural bond orbitals of the reagents and has been complemented with a second‐order perturbation theory analysis. The adaptive natural density partitioning method has also been used to verify the results and conclusions of the analysis. The concordant results of the three methodologies provide us with a better understanding of the reaction mechanism involving the torquoselectivity. We also carried out the analysis in both directions of the reaction to verify the conclusions obtained.