Orbital symmetry control in the nitrone-oxaziridine system. Nitrone photostationary states

Abstract

Recent the orbital symmetry rules have been shown to apply to hetero-atom systems such as nitrone thermal cycloaddition reactions and the thermal and photochemical aziridine ring cleavage at the C-C bond. The concerted photocyclization is disrotatory and the reverse thermal cleavage is conrotatory in these molecules with four {pi} electrons. In contrast to the azomethine ylide-aziridine system, the stereochemistry of the nitrone photocyclization to oxaziridine can only be observed on carbon and nitrogen atoms because the oxygen atom has lone pair electrons instead of substituents. For the reverse thermal ring opening of oxaziridine to the nitrone, the two possible conrotatory motions of C-O bond cleavage should result in a mixture of the cis and trans-isomers of the nitrone, in contrast to the photoclosure which should be stereospecific.