Oxidative Arene Ring-Opening of Benzylic Alcohols

Abstract

Arene ring-opening (ARO) reaction via C–C bond cleavage remains a formidable challenge due to the exceptional thermodynamic stability of aromatic frameworks. Inspired by enzymatic lignin degradation in nature, we report an oxidative strategy that enables arene ring-opening of benzylic alcohols under mild conditions. Using hydrogen peroxide as oxidant and 2-nitro-4-(trifluoromethyl)benzeneseleninic acid as the catalyst, we achieved the efficient conversion of benzylic alcohols into muconolactone or muconic acid derivatives, which contain multiple functional handles enabling diverse downstream derivatizations. Both of the exocyclic C–C bonds and the arene ring C–C bonds in benzylic alcohols were cleaved through the present Se-catalytic tandem oxidation and rearrangement processes.