Pd/C promotes C–H bond activation and oxidation of p-hydroxybenzoate during hydrogenolysis of poplar
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, f...
Saved in:
| Main Authors: | , , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
Nature Portfolio
2025-06-01
|
| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-025-60270-x |
| Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
| _version_ | 1849469924134617088 |
|---|---|
| author | Canan Sener Vitaliy I. Timokhin Jan Hellinger John Ralph Steven D. Karlen |
| author_facet | Canan Sener Vitaliy I. Timokhin Jan Hellinger John Ralph Steven D. Karlen |
| author_sort | Canan Sener |
| collection | DOAJ |
| description | 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. |
| format | Article |
| id | doaj-art-24999a3ef6a945a083bf8824c8eafa2d |
| institution | Kabale University |
| issn | 2041-1723 |
| language | English |
| publishDate | 2025-06-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj-art-24999a3ef6a945a083bf8824c8eafa2d2025-08-20T03:25:19ZengNature PortfolioNature Communications2041-17232025-06-011611810.1038/s41467-025-60270-xPd/C promotes C–H bond activation and oxidation of p-hydroxybenzoate during hydrogenolysis of poplarCanan Sener0Vitaliy I. Timokhin1Jan Hellinger2John Ralph3Steven D. Karlen4Wisconsin Energy Institute, University of WisconsinWisconsin Energy Institute, University of WisconsinWisconsin Energy Institute, University of WisconsinWisconsin Energy Institute, University of WisconsinWisconsin Energy Institute, University of WisconsinAbstract 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.https://doi.org/10.1038/s41467-025-60270-x |
| spellingShingle | Canan Sener Vitaliy I. Timokhin Jan Hellinger John Ralph Steven D. Karlen Pd/C promotes C–H bond activation and oxidation of p-hydroxybenzoate during hydrogenolysis of poplar Nature Communications |
| title | Pd/C promotes C–H bond activation and oxidation of p-hydroxybenzoate during hydrogenolysis of poplar |
| title_full | Pd/C promotes C–H bond activation and oxidation of p-hydroxybenzoate during hydrogenolysis of poplar |
| title_fullStr | Pd/C promotes C–H bond activation and oxidation of p-hydroxybenzoate during hydrogenolysis of poplar |
| title_full_unstemmed | Pd/C promotes C–H bond activation and oxidation of p-hydroxybenzoate during hydrogenolysis of poplar |
| title_short | Pd/C promotes C–H bond activation and oxidation of p-hydroxybenzoate during hydrogenolysis of poplar |
| title_sort | pd c promotes c h bond activation and oxidation of p hydroxybenzoate during hydrogenolysis of poplar |
| url | https://doi.org/10.1038/s41467-025-60270-x |
| work_keys_str_mv | AT canansener pdcpromoteschbondactivationandoxidationofphydroxybenzoateduringhydrogenolysisofpoplar AT vitaliyitimokhin pdcpromoteschbondactivationandoxidationofphydroxybenzoateduringhydrogenolysisofpoplar AT janhellinger pdcpromoteschbondactivationandoxidationofphydroxybenzoateduringhydrogenolysisofpoplar AT johnralph pdcpromoteschbondactivationandoxidationofphydroxybenzoateduringhydrogenolysisofpoplar AT stevendkarlen pdcpromoteschbondactivationandoxidationofphydroxybenzoateduringhydrogenolysisofpoplar |