Metal Catalyst‐Free Oxidative C−C Bond Cleavage of a Lignin Model Compound by H2O2 in Formic acid

Abstract Selective cleavage of the β‐O‐4 ether bond of lignin to produce aromatics is one of the most important topics for the sustainable production of chemicals from biomass. A simple system has been developed for Cα−Cβ bond cleavage of a β‐O‐4 ketone‐structured lignin model compound (LMC) by H2O2 in formic acid under metal catalyst‐free conditions. By using this simple system, with H2O2, formic acid, and mineral acid catalyst, over 90 % product yield is achieved in 6 h at room temperature. The reaction proceeds through the classic Baeyer–Villiger oxidation and in situ‐generated performic acid serves as the key oxidant. The cleavage of alcoholic LMCs by using the presented method in a two‐step process is also demonstrated.