The Effect of Proximal Functionality on the Allylic Azide Equilibrium

This report describes an investigation into the effect that proximal functionality has on the allylic azide equilibrium. We report 16 allylic azides with varied functionality from three subclasses. We observe a correlation of % branched azide to the pKa of the OR group. We also observe that RN–H azides have a higher % branched azide relative the corresponding RN–Bn compound. These two effects combine to describe the observed equilibrium for the known compound hydroxy-crotyl azide. DFT calculations support several stereoelectronic effects that contribute to the relative energetics.