Insight into the intramolecular interactions of trans-2-azidocycloalk-3-en-1-ols and trans-2-azidocycloalk-3-en-1-yl acetates: A theoretical study

In this study, dedicated to Prof. Dr. Yaşar Sütbeyaz (1950–2016), 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 ωB97XD with the 6-31+G(d,p) basis set. These allylic azides stabilized by intramolecular OH⋯N and CH⋯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. [Display omitted] •Intramolecular interactions in allylic azides having six-to eight-membered rings were investigated by DFT calculations.•Two new azidocycloalkenyl acetates were synthesized.•The reason why Winstein rearrangement did not occur in the cyclic allylic azides was supported by theoretical calculations.•Frontier molecular orbital analysis, NBO and MEP analysis of the allylic azides were calculated.