Chiral diastereomers of 2-isopropyl-5-methyl-6-(4-phenyl)benzylcyclohex-2-enone and their isomer 2-(4-phenylbenzyl)-3-methyl-6-isopropylcyclohex-2-enone, which are products of an acid-catalyzed intramolecular rearrangement of 3R,6R-2-(4-phenylbenzylidene)-3-methyl-6-isopropylcyclohexanone, were investigated to show that conformational analysis by molecular mechanics and 1H NMR spectroscopy permits an integrated solution of three structural problems: double bond location in an aliphatic ring for isomeric products; determination of the stereochemical configuration for the two diastereomers; evaluation of the conformational equilibrium between the diastereomers. Based on the results of calculations, this is achieved by estimating the configuration- and conformation-sensitive proton spin–spin coupling constants of the cyclohexenone ring for alternative structures and correlating them with 1H NMR data.