In this study, dedicated to Prof. Dr. Yasar Sutbeyaz (1950e2016), intramolecular interactions in (1S(R),2S(R))-2-azidocycloalk-3-en-1-ols and (1S(R),2S(R))-2-azidocycloalk-3-en-1-yl acetates consisting of six-to eight-membered rings were investigated by molecular spectroscopy and density functional theory calculations including three different functional levels, B3LYP, M06-2X and omega B97XD with the 6-31 +G(d,p) basis set. These allylic azides stabilized by intramolecular OH center dot center dot center dot N and CH center dot center dot center dot N interactions did not cause the Winstein rearrangement known as the 1,3-allylic azide rearrangement or [3,3]-sigmatropic rearrangement. The results of the structural parameters, relative total energies, natural bond orbital analysis of donor-acceptor interactions and charges on the atoms support why the Winstein rearrangement does not occur. The quantum chemical reactivity identifiers and molecular electrostatic potential were analyzed using the M062X/6-31+G(d,p) basis set. (c) 2021 Elsevier Ltd. All rights reserved.