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

Omolabake, Surajudeen; Hofsommer, Dillon T.; Mains, Kathryn M.; Palumbo, Chad T.; Rigo, Davide; Werner, Allison Z.; Beckham, Gregg T.; Stahl, Shannon S.

doi:10.1002/anie.202515588

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

Journal Article · Mon Nov 17 00:00:00 UTC 2025 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.202515588· OSTI ID:3018721

Omolabake, Surajudeen ^[1]; Hofsommer, Dillon T. ^[1]; Mains, Kathryn M. ^[2]; Palumbo, Chad T. ^[3]; Rigo, Davide ^[2]; ^[2]; ^[2]; ^[1]

University of Wisconsin‐Madison, WI (United States)
National Renewable Energy Laboratory (NREL), Golden, CO (United States); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
National Renewable Energy Laboratory (NREL), Golden, CO (United States)

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 O2 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.

View Accepted Manuscript (DOE)

Research Organization:: Alliance for Energy Innovation, LLC, Golden, CO (United States); Great Lakes Bioenergy Research Center (GLBRC), Madison, WI (United States); National Laboratory of the Rockies (NLR), Golden, CO (United States); University of Wisconsin-Madison, WI (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Bioenergy Technologies Office (BETO); USDOE Office of Science (SC), Biological and Environmental Research (BER)

Grant/Contract Number:: AC36-08GO28308; SC0018409

Other Award/Contract Number:: ERKP886

OSTI ID:: 3018721

Alternate ID(s):: OSTI ID: 3003248
OSTI ID: 3014859

Report Number(s):: NLR/JA--2A00-96429

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 2 Vol. 65; ISSN 1521-3773; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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09 BIOMASS FUELS
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Aerobic oxidation
C-C bond cleavage
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C–C bond cleavage
C─C bond cleavage
Lignin monomers
Lignin oligomer
aerobic oxidation
catalysis
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Cu‐Catalyzed Aerobic Oxidative C─C Cleavage in Lignin‐Derived Oligomers and Biological Funneling of the Monomeric Products

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