Theoretical investigation of the substituent effects in the conformational isomerism of bromoalkoxycyclohexanes

► The conformational isomerism of a series of bromoalkoxycyclohexanes has been determined computationally. ► Isodesmic reactions were carried out to evaluate the preferred orientation of Br in an alkoxycyclohexane. ► Intramolecular interactions induced by substituents rule the conformational preferences.