Pd/C promotes C–H bond activation and oxidation of p-hydroxybenzoate during hydrogenolysis of poplar

Canan Sener, Vitaliy I. Timokhin, Jan Hellinger, John Ralph and Steven D. Karlen ()
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Canan Sener: University of Wisconsin
Vitaliy I. Timokhin: University of Wisconsin
Jan Hellinger: University of Wisconsin
John Ralph: University of Wisconsin
Steven D. Karlen: University of Wisconsin

Nature Communications, 2025, vol. 16, issue 1, 1-8

Abstract: Abstract Hydrogenolysis of lignin generates a portfolio of products, the yields of which are generally calculated using a subset of phenolic monomers that are dependent on the lignin composition, product distribution, and analytical technique. Some lignins are naturally γ-acylated; poplar lignins, for example, have p-hydroxybenzoate groups on 1–15% of their syringyl subunits. Upon hydrogenolysis, it is generally assumed that the p-hydroxybenzoate is cleaved before the deacylated lignin is depolymerized. Hydrogenolysis of model γ-p-hydroxybenzoylated β-aryl ethers do not, however, produce the deacylated β-aryl ether intermediates, as was previously conjectured; products instead derive from palladium-assisted reactions on the cinnamyl p-hydroxybenzoates resulting in initial β-ether cleavage. The p-hydroxybenzoate moiety itself also undergoes carboxylate-assisted palladium-catalyzed C–H bond activation to form the 2,4-dihydroxybenzoate, that subsequently converts to the 2,4-dihydroxycyclohex-1-enoate. These details underscore previously unrecognized pathways and products that are key to understanding the different hydrogenolysis product distributions from naturally acylated lignins that are prevalent biomass-conversion feedstocks.

Date: 2025
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DOI: 10.1038/s41467-025-60270-x

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