Cu‐Catalyzed Aerobic Oxidative C─C Cleavage in Lignin‐Derived Oligomers and Biological Funneling of the Monomeric Products

Abstract Existing methods for lignin deconstruction to aromatic monomers primarily cleave carbon–oxygen bonds within the polymer, resulting in sub‐optimal monomer yields and formation of oligomers that retain intact carbon–carbon bonds. Here, we demonstrate that copper‐catalyzed aerobic oxidation under aqueous alkaline conditions promotes oxidative cleavage of carbon–carbon bonds in lignin oligomers derived from reductive catalytic fractionation (RCF) of pine and poplar biomass. Fundamental insights are gained from reactions of model compounds that resemble subunits present in RCF oligomers. Optimal results are achieved in a flow reactor that provides precise control over O 2 delivery, temperature, and reaction residence time. The Cu‐catalyzed aerobic oxidation conditions access aromatic monomers in 19 and 34 wt% monomer yields, respectively, from pine‐ and poplar‐derived RCF oligomers. Overall, the sequence consisting of biomass RCF into monomers and oligomers followed by oxidative deconstruction of the RCF oligomers generates substantially higher yields of aromatic monomers from lignin. Engineered strains of Pseudomonas putida support biological funneling of the oligomer‐derived oxygenated aromatic compounds into cis , cis ‐muconic acid from pine or 2‐pyrone‐4,6‐dicarboxylic acid from poplar.