Mechanisms of the Aerobic Oxidation of Alcohols to Aldehydes and Ketones Catalysed under Mild Conditions by Persistent and Non-Persistent Nitroxide Radicals and Transition Metal Salts – Polar, Enthalpic and Captodative Effects

The oxidation of alcohols to aldehydes and ketones by air or oxygen under mild conditions (room temperature and atmospheric pressure), catalysed by persistent and non-persistent nitroxyl radicals in combination with transition metal salts, appears to be the most convenient of the numerous processes developed for these purposes. The thermochemistry, the kinetics, and the Hammett correlations have allowed us to establish, on a quantitative basis, the fundamental difference between the oxidation catalysed by persistent and non-persistent nitroxyl catalysts. In the latter case, an interesting significant captodative effect is displayed for the first time for the oxidation of substituted benzyl alcohols; the importance of enthalpic and polar effects is emphasised