Copper-catalyzed C–C bond cleavage coupling with C≡N bond formation toward mild synthesis of lignin-based benzonitriles  

作　　者：Qi Luo Shenglong Tian Qian Qiang Fei song Wentao Su Haiyan He Qingda An Changzhi Li 

机构地区：[1]Liaoning Key Lab of Lignocellulose Chemistry and BioMaterials,Liaoning Collaborative Innovation Center for Lignocellulosic Biorefinery,School of Light Industry and Chemical Engineering,Dalian Polytechnic University,Dalian 116034,China [2]CAS Key Laboratory of Science and Technology on Applied Catalysis,Dalian Institute of Chemical Physics,Chinese Academy of Sciences,Dalian 116023,China [3]University of Chinese Academy of Science,Beijing 100049,China

出　　处：《Journal of Environmental Sciences》2025年第5期505-515,共11页环境科学学报(英文版)

基　　金：supported by the National Key R&D Program of China(No.2023YFA1507902);the National Natural Science Foundation of China(Nos.21721004 and 21878288);the science and technology bureau of Dalian city(No.2021RT04);the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDB17020100).

摘　　要：N-participated lignin depolymerization is of great importance for the transformation of waste lignin into value-added chemicals.The vast majority of developed strategies employ organic amines as nitrogen source,and considerablemethods rely on excessive use of strong base,which suffers severe environmental issues.Herein,benzonitrile derivatives are synthesized from oxidized ligninβ-O-4 model compounds in the presence of solid nitrogen source(NH_(4))_(2)CO_(3)under mild,base-free conditions over commercially available copper catalyst.Mechanism studies suggest the transformation undergoes a one-pot,highly coupled cascade reaction path involving oxidative C-C bond cleavage and in-situ formation of C≡N bond.Of which,Cu(OAc)2 catalyzes the transfer of hydrogen from C_(β)(C_(β)-H)to C_(α),leading to the cleavage of C_(α)-C_(β)bonds to offer benzaldehyde derivative,this intermediate then reacts in-situ with(NH_(4))_(2)CO_(3)to afford the targeted aromatic nitrile product.Tetrabutylammonium iodide(TBAI),acting as a promoter,plays a key role in breaking the C_(α)-C_(β)bonds to form the intermediate benzaldehyde derivative.With this protocol,the feasibility of the production of value-added syringonitrile from birchwood lignin has been demonstrated.This transformation provides a sustainable approach to benzonitrile chemicals from renewable source of lignin.

关 键 词：LIGNIN β-O-4 model compounds Benzonitrile derivatives Copper catalyst Mild conditions 

分 类 号：X592[环境科学与工程—环境工程]