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

IF 5.9 2区 环境科学与生态学 Q1 ENVIRONMENTAL SCIENCES
Qi Luo , Shenglong Tian , Qian Qiang , Fei song , Wentao Su , Haiyan He , Qingda An , Changzhi Li
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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.

Abstract Image

铜催化 C-C 键裂解与 C N 键形成耦合,实现木质素基苯腈的温和合成
氮参与木质素解聚对于将废弃木质素转化为高附加值化学品非常重要。绝大多数已开发的策略都采用有机胺作为氮源,而相当多的方法都依赖于过量使用强碱,这带来了严重的环境问题。在此,研究人员在温和、无碱的条件下,利用市售铜催化剂,在固体氮源 (NH4)2CO3 的存在下,从氧化木质素 β-O-4 模型化合物中合成了苯甲腈衍生物。机理研究表明,该转化过程经历了一个一锅式、高度耦合的级联反应路径,涉及 C-C 键的氧化裂解和 CN 键的原位形成。其中,Cu(OAc)2 催化氢从 Cβ(Cβ-H)转移到 Cα,导致 Cα-Cβ 键裂解,生成苯甲醛衍生物,然后该中间体与 (NH4)2CO3 原位反应,生成目标芳香族腈产物。四丁基碘化铵(TBAI)作为一种促进剂,在断裂 Cα-Cβ 键形成中间体苯甲醛衍生物的过程中发挥了关键作用。通过这一方案,证明了利用桦木木质素生产高附加值丁香腈的可行性。这种转化提供了一种从可再生木质素来源生产苯甲腈化学品的可持续方法。
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来源期刊
Journal of Environmental Sciences-china
Journal of Environmental Sciences-china 环境科学-环境科学
CiteScore
13.70
自引率
0.00%
发文量
6354
审稿时长
2.6 months
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.
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