Qi Luo , Shenglong Tian , Qian Qiang , Fei song , Wentao Su , Haiyan He , Qingda An , Changzhi Li
{"title":"Copper-catalyzed C–C bond cleavage coupling with CN bond formation toward mild synthesis of lignin-based benzonitriles","authors":"Qi Luo , Shenglong Tian , Qian Qiang , Fei song , Wentao Su , Haiyan He , Qingda An , Changzhi Li","doi":"10.1016/j.jes.2024.03.031","DOIUrl":null,"url":null,"abstract":"<div><p>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 considerable methods rely on excessive use of strong base, which suffers severe environmental issues. Herein, benzonitrile derivatives are synthesized from oxidized lignin β-O-4 model compounds in the presence of solid nitrogen source (NH<sub>4</sub>)<sub>2</sub>CO<sub>3</sub> 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 <em>in-situ</em> formation of C<img>N bond. Of which, Cu(OAc)<sub>2</sub> catalyzes the transfer of hydrogen from C<sub>β</sub> (C<sub>β</sub>-H) to C<sub>α</sub>, leading to the cleavage of C<sub>α</sub>-C<sub>β</sub> bonds to offer benzaldehyde derivative, this intermediate then reacts <em>in-situ</em> with (NH<sub>4</sub>)<sub>2</sub>CO<sub>3</sub> to afford the targeted aromatic nitrile product. Tetrabutylammonium iodide (TBAI), acting as a promoter, plays a key role in breaking the C<sub>α</sub>-C<sub>β</sub> 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.</p></div>","PeriodicalId":15788,"journal":{"name":"Journal of Environmental Sciences-china","volume":"151 ","pages":"Pages 505-515"},"PeriodicalIF":5.9000,"publicationDate":"2024-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Environmental Sciences-china","FirstCategoryId":"93","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S1001074224001475","RegionNum":2,"RegionCategory":"环境科学与生态学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"ENVIRONMENTAL SCIENCES","Score":null,"Total":0}
引用次数: 0
Abstract
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 considerable methods rely on excessive use of strong base, which suffers severe environmental issues. Herein, benzonitrile derivatives are synthesized from oxidized lignin β-O-4 model compounds in the presence of solid nitrogen source (NH4)2CO3 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 CN bond. Of which, Cu(OAc)2 catalyzes the transfer of hydrogen from Cβ (Cβ-H) to Cα, leading to the cleavage of Cα-Cβ bonds to offer benzaldehyde derivative, this intermediate then reacts in-situ with (NH4)2CO3 to afford the targeted aromatic nitrile product. Tetrabutylammonium iodide (TBAI), acting as a promoter, plays a key role in breaking the Cα-Cβ 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.
期刊介绍:
The Journal of Environmental Sciences is an international journal started in 1989. The journal is devoted to publish original, peer-reviewed research papers on main aspects of environmental sciences, such as environmental chemistry, environmental biology, ecology, geosciences and environmental physics. Appropriate subjects include basic and applied research on atmospheric, terrestrial and aquatic environments, pollution control and abatement technology, conservation of natural resources, environmental health and toxicology. Announcements of international environmental science meetings and other recent information are also included.