Photocatalytic Cleavage of Aryl Ether in Modified Lignin to Non-phenolic Aromatics,ACS Catalysis

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Photocatalytic Cleavage of Aryl Ether in Modified Lignin to Non-phenolic Aromatics
ACS Catalysis ( IF 11.3 ) Pub Date : 2019-08-14 00:00:00 , DOI: 10.1021/acscatal.9b02719
Hongji Li _{1,

2} , Anon Bunrit ₁ , Jianmin Lu ₁ , Zhuyan Gao _{1,

2} , Nengchao Luo _{1,

2} , Huifang Liu ₁ , Feng Wang ₁

Affiliation

Depolymerization of lignin meets the difficulty in cleaving the robust aryl ether bond. Herein, through installing an internal nucleophile in the β-O-4′ linkage, the selective cleavage of aryl ether was realized by the intramolecular substitution on aryl rings affording non-phenolic arylamine products. In particular, nitrogen-modified lignin models and lignin samples were employed to generate the iminyl radical under photocatalytic reduction, which acted as the internal nucleophile inducing aryl migration from O to the N atom. The following hydrolysis released primary arylamines and α-hydroxy ketones. Mechanism studies including electron spin resonance (ESR), fluorescence quenching experiments, and density functional theory (DFT) calculations proved the aryl migration pathway. This method enables access to non-phenolic arylamine products from lignin conversion.

中文翻译：

改性木质素中芳醚的光催化裂解为非酚芳烃

木质素的解聚遇到了裂解牢固的芳基醚键的困难。在此，通过在β-O-4'键上安装内部亲核试剂，通过在芳环上进行分子内取代而实现芳基醚的选择性裂解，从而得到非酚性芳胺产物。特别地，使用氮改性的木质素模型和木质素样品在光催化还原下产生亚胺基，其充当内部亲核试剂，诱导芳基从O原子迁移到N原子。随后的水解释放出伯芳基胺和α-羟基酮。包括电子自旋共振（ESR），荧光猝灭实验和密度泛函理论（DFT）计算在内的机理研究证明了芳基迁移途径。

更新日期：2019-08-14

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