Supramolecularly modulated carbon-centered radicals: toward selective oxidation from benzyl alcohol to aldehyde

The reactivity of ketyl radicals and benzoyl radicals, two key intermediates of photo-induced oxidation of benzyl alcohol, can be stabilized by the host-guest interaction of the radicals with cucurbit[7]uril. As a result, the selectivity of photo-induced oxidation from benzyl alcohol to aldehyde is significantly improved by diminishing side reactions and inhibiting the generation of carboxylic acid products. This work presents a new route to modulate the reactivity of radical intermediates, enriching the chemistry of supramolecular intermediates and the toolbox of supramolecular catalysis. Host-guest interaction of cucurbit[7]uril is used to adjust the reactivity of ketyl radicals and benzoyl radicals, therefore enhancing the aldehyde selectivity of photo-induced oxidation of benzyl alcohol.