Mechanisms and consequences of oxygen transfer reactions

Abstract

The geometry about oxygen in the transition-state structures for oxygen transfers from a nitrone to phosphorous, from a percarboxylic acid to a carbon-carbon double bond, and from an N-sulfonyl oxaziridine to a carbon-carbon double bond have been evaluated by the endocyclic restriction test. The former can proceed at an oblique angle, while the latter two require a large angle between the entering and leaving groups on oxygen. This information is used to determine the mechanism of the aldehyde-dependent oxygen transfer from molecular oxygen to a carbon-carbon double bond.