The quantum-chemical modeling of the reaction of nitroso oxides with olefins

The density functional theory method was used to localize minima on the singlet potential energy surfaces of the nitroso oxide—ethylene, phenylnitroso oxide—tetramethylethylene, phenylnitroso oxide—hexene-1, and phenylnitroso oxide-styrene systems and on the triplet potential energy surfaces of the nitroso oxide—ethylene and phenylnitroso oxide-hexene-1 systems. The energetically favorable path was found to be that of (3 + 2) cycloaddition with the formation of five-membered rings, which decomposed into nitrone and carbonyl compound with the simultaneous dissociation of the C-C and C-O bonds. The influence of cis-trans isomerism of nitroso oxides on their reactivity with respect to olefins was studied.