Insight into the factors controlling the equilibrium of allylic azides

Several allylic azides with different double bond substitutions were studied to understand the factors, governing their equilibrium using density functional theory along with the quantum theory of atoms in molecules, non-covalent interactions and natural bond orbital approaches. The results showed that the hydroxyl group or heteroatoms in allylic azides interact with the molecule through an electrostatic weak interaction in each pair of regioisomers. The equilibrium shifts of substituted allylic azides, compared to non-substituted allylic azides, were not attributed to the presence of specific interactions, such as hydrogen bonds. The observed equilibrium shifts stemmed mainly from the strengthening and weakening of negative hyperconjugative interactions, which were affected by the weak interaction involving the proximal substituent in each regioisomer. A good linear correlation was obtained between the hyperconjugative energies of pi C?C ->sigma*Z(b) interactions and the calculated percentages of the secondary azide and tertiary azide in the equilibrium mixture. Also, the effect of the aromatic ring substituent was analysed using such approaches. This study not only provides insights into the factors controlling the stabilities of the substituted allylic azides, but also settles the basis to predict the regioisomer predominance in the equilibrium mixture.