For the primary azide 1i, G # for the abstraction of proton process (TS11-3i, 19.8 kcal/mol) was significantly lower than that for the sigmatropic reaction. As a result, the difference between both energies was 7.0 kcal/mol, which is similar to that observed for the reaction with secondary azide 1h. Starting from the primary azide 1i our results for the Banert cascade will lead to the prototropic product 7i, that is good an agreement with the reported reaction that give a 20:1 (7i:6i). The first step of the reaction involved the removal of a propargylic proton by methoxide oxygen, resulting in the formation of intermediates IN1-3x with high energy compared to the reactant complexes. These intermediates are highly reactive due to the presence of an anionic carbon, which makes them prone to accepting a proton from the solvent, thus facilitating the second step of the prototropic reaction, and leading to the formation of allenyl azides 3x. The low energy barriers (1.8-1.1 kcal/mol) or absence of barriers (for x = f-i) further support the efficiency of this reaction.