In this work, a DFT study of both pathways of the Banert cascade from several propargylic azides, was performed in order to gain a better understanding on the divergent mechanism and rationalize the experimental results. For the prototropic pathway, the methoxide ion was taken as nucleophile. In addition, we have performed a quantum theory of atoms in molecules (QTAIM) and natural bond orbital (NBO) analysis to gain a deeper insight into factor controlling the reactions and to locate some indicator that allow predicting the course of the reaction.