Efforts to produce aromatic monomers through catalytic lignin depolymerization have historically focused on aryl–ether bond cleavage. A large fraction of aromatic monomers in lignin, however, are linked by various carbon–carbon (C–C) bonds that are more challenging to cleave and limit the yields of aromatic monomers from lignin depolymerization. Here, we report a catalytic autoxidation method to cleave C–C bonds in lignin-derived dimers and oligomers from pine and poplar. The method uses manganese and zirconium salts as catalysts in acetic acid and produces aromatic carboxylic acids as primary products. The mixtures of the oxygenated monomers are efficiently converted to cis,cis -muconic acid in an engineered strain of Pseudomonas putida KT2440 that conducts aromatic O -demethylation reactions at the 4-position. This work demonstrates that autoxidation of lignin with Mn and Zr offers a catalytic strategy to increase the yield of valuable aromatic monomers from lignin.
Palumbo, Chad T., et al. "Catalytic carbon–carbon bond cleavage in lignin via manganese–zirconium-mediated autoxidation." Nature Communications, vol. 15, no. 1, Jan. 2024. https://doi.org/10.1038/s41467-024-45038-z
Palumbo, Chad T., Gu, Nina X., Bleem, Alissa C., Sullivan, Kevin P., Katahira, Rui, Stanley, Lisa M., Kenny, Jacob K., Ingraham, Morgan A., Ramirez, Kelsey J., Haugen, Stefan J., Amendola, Caroline R., Stahl, Shannon S., & Beckham, Gregg T. (2024). Catalytic carbon–carbon bond cleavage in lignin via manganese–zirconium-mediated autoxidation. Nature Communications, 15(1). https://doi.org/10.1038/s41467-024-45038-z
@article{osti_2283106,
author = {Palumbo, Chad T. and Gu, Nina X. and Bleem, Alissa C. and Sullivan, Kevin P. and Katahira, Rui and Stanley, Lisa M. and Kenny, Jacob K. and Ingraham, Morgan A. and Ramirez, Kelsey J. and Haugen, Stefan J. and others},
title = {Catalytic carbon–carbon bond cleavage in lignin via manganese–zirconium-mediated autoxidation},
annote = {Abstract Efforts to produce aromatic monomers through catalytic lignin depolymerization have historically focused on aryl–ether bond cleavage. A large fraction of aromatic monomers in lignin, however, are linked by various carbon–carbon (C–C) bonds that are more challenging to cleave and limit the yields of aromatic monomers from lignin depolymerization. Here, we report a catalytic autoxidation method to cleave C–C bonds in lignin-derived dimers and oligomers from pine and poplar. The method uses manganese and zirconium salts as catalysts in acetic acid and produces aromatic carboxylic acids as primary products. The mixtures of the oxygenated monomers are efficiently converted to cis,cis -muconic acid in an engineered strain of Pseudomonas putida KT2440 that conducts aromatic O -demethylation reactions at the 4-position. This work demonstrates that autoxidation of lignin with Mn and Zr offers a catalytic strategy to increase the yield of valuable aromatic monomers from lignin. },
doi = {10.1038/s41467-024-45038-z},
url = {https://www.osti.gov/biblio/2283106},
journal = {Nature Communications},
issn = {ISSN 2041-1723},
number = {1},
volume = {15},
place = {United Kingdom},
publisher = {Nature Publishing Group},
year = {2024},
month = {01}}
National Renewable Energy Laboratory (NREL), Golden, CO (United States); Univ. of Wisconsin, Madison, WI (United States)
Sponsoring Organization:
USDOE; USDOE Office of Energy Efficiency and Renewable Energy (EERE); USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Biological and Environmental Research (BER)