Exploration and Exploitation of Synthetic Use of Oxoammonium Ions in Alcohol Oxidation

Novel synthetic uses of oxoammonium ions enabling facile and efficient oxidation of several classes of alcohols to their related carbonyl compounds have been exploited on the basis of two strategies: (i) modifying the molecular framework of the oxoammonium ion, and (ii) enhancing its reactive nature by altering the counter ion. The reaction systems developed allow: (1) efficient oxidation of sterically crowded secondary alcohols to ketones; (2) facile, one-pot oxidation of primary alcohols to carboxylic acids; (3) oxidative rearrangement of tertiary allylic alcohols to beta-substituted alpha,beta-unsaturated carbonyl compounds under transition-metal-free conditions.