Selective lignin arylation for biomass fractionation and benign bisphenols

• 成果类型: Article
• 署名作者: Li, Ning; Yan, Kexin; Rukkijakan, Thanya; Liang, Jiefeng; Liu, Yuting; Wang, Zhipeng; Nie, Heran; Muangmeesri, Suthawan; Castiella-Ona, Gonzalo; Pan, Xuejun; Zhou, Qunfang; Jiang, Guibin; Zhou, Guangyuan; Ralph, John; Samec, Joseph S. M.; Wang, Feng
• 署名单位: Chinese Academy of Sciences; Dalian Institute of Chemical Physics, CAS; Stockholm University; Chinese Academy of Sciences; University of Chinese Academy of Sciences, CAS; Chinese Academy of Sciences; Research Center for Eco-Environmental Sciences (RCEES), CAS; Shandong University; University of Wisconsin System; University of Wisconsin Madison; University of Wisconsin System; University of Wisconsin Madison
• 刊物名称: Nature
• ISSN/ISSBN: 0028-4160
• DOI: 10.1038/s41586-024-07446-5
• 发表日期: 2024-06-13
• 页码: 381-+
• 关键词: depolymerization

摘要

Lignocellulose is mainly composed of hydrophobic lignin and hydrophilic polysaccharide polymers, contributing to an indispensable carbon resource for green biorefineries(1,2). When chemically treated, lignin is compromised owing to detrimental intra- and intermolecular crosslinking that hampers downstream process(3,4). The current valorization paradigms aim to avoid the formation of new C-C bonds, referred to as condensation, by blocking or stabilizing the vulnerable moieties of lignin(5-7). Although there have been efforts to enhance biomass utilization through the incorporation of phenolic additives(8,9), exploiting lignin's proclivity towards condensation remains unproven for valorizing both lignin and carbohydrates to high-value products. Here we leverage the proclivity by directing the C-C bond formation in a catalytic arylation pathway using lignin-derived phenols with high nucleophilicity. The selectively condensed lignin, isolated in near-quantitative yields while preserving its prominent cleavable beta-ether units, can be unlocked in a tandem catalytic process involving aryl migration and transfer hydrogenation. Lignin in wood is thereby converted to benign bisphenols (34-48 wt%) that represent performance-advantaged replacements for their fossil-based counterparts. Delignified pulp from cellulose and xylose from xylan are co-produced for textile fibres and renewable chemicals. This condensation-driven strategy represents a key advancement complementary to other promising monophenol-oriented approaches targeting valuable platform chemicals and materials, thereby contributing to holistic biomass valorization.