Oxidative Amination Ring Cleavage of Catechols for Muconic Acid Mononitriles

An efficient oxidative ring-opening reaction of catechols to afford cis,cis-muconic acid mononitriles was established under mild conditions with a broad substrate scope. The transformation enables most catechols containing asymmetric substituents to generate a single or major product. The reaction can be scaled to gram quantities, highlighting its practical utility. Experimental studies and density functional theory calculations support a mechanism involving pyrocatechol oxidation, quinone-amine condensation, nucleophilic addition, and subsequent aromatic ring cleavage.