Torquoselectivity has explained diasteromeric preferences of a number electrocyclic ring openings. The quantum theory of atoms in molecules (QTAIM), the electron localizability indicator (ELI-D), and the interacting quantum atoms (IQA) energy partition method are used to evaluate qualitatively and quantitatively the atomic interactions behind the torquoselectivity of a series of 3-substituted cydobutenes. ELI-D topology and IQA energies show that the interaction between the distal terminus carbon atom of cyclobutene (C4) with the substituent at C3 (RS) in the transition state governs torquoselectivities. In the case of 3-borylcyclobutene, this interaction is so strong that a protocovalent bond is actually formed between B5 and C4. The evaluation of the interatomic energies allowed us to identify an additional interaction that contribute to a minor extent to the stabilization of the TS. Despite the fact that C4,R5 interaction is the main cause of the torquoselectivity, a bonding path (BP) between these two atoms was not observed. However, the lack of a BP between C4 and R5 does not mean that the topology of the electron density was not affected by the interaction of these two atoms. Surprisingly, we found a strong correlation between the density at the bond critical point (BCP) and the BP shape of C3 C4 breaking bond with the observed activation energies and torquoselectivities.