摘要
芳基氯化物是一类重要的有机化合物,在化学合成、药物改性等领域中有着广泛的应用,通常由强氧化性氯源和芳烃在高温高压下形成。苛刻的反应条件常伴随区域选择性较差、副反应多等问题。随着有机合成方法学的发展,芳基氯化物也可以通过其它官能团转化形成,但仍需要进行预官能团化。相比之下,原子经济性最高的方法是芳烃C(sp^(2))—H键的直接氯化。通过定向活化芳环C—H键,能够以较高的选择性得到目标产物的同时避免官能团的限制,温和的反应条件有效地避免了副产物的产生。近些年,芳环C(sp^(2))—H键直接氯化方法有了很大的发展,出现了许多绿色、高效、适用范围广的合成方法。本文总结了近十年芳烃C(sp^(2))—H氯化反应在过渡金属催化、光催化、有机催化和电催化方面的研究进展,对不同方法的反应条件、底物适用范围、产率和机理等进行讨论。
Aryl chlorides are an important class of organic compounds with broad applications in chemical synthesis,pharmaceutical modification,and related fields.They are typically synthesized using strongly oxidizing chlorinating agents and aromatic hydrocarbons under high-temperature and highpressure conditions,and the harsh reaction conditions are often accompanied by issues such as poor regioselectivity and numerous side reactions.With the advancement of organic synthetic methodologies,Aryl chlorides can also be formed through functional group transformations,although these approaches still require pre-functionalization steps.Among these approaches,the most atom-economical method involves the direct chlorination of aromatic C(sp^(2))—H bonds.Through the directed activation of aromatic C—H bonds,it is possible to achieve high selectivity for the target product while circumventing functional group limitations.The mild reaction conditions effectively suppress the generation of byproducts.In recent years,significant progress has been made in direct chlorination methods for aromatic C(sp^(2))—H bonds,with the emergence of numerous green,highly efficient,and versatile synthetic approaches that demonstrate broad applicability.This review summarizes research advances in the field of transition metal catalysis,photocatalysis,organocatalysis and electrocatalysis of aromatic C(sp^(2))—H chlorination over the past decade,with a focus on comparing reaction conditions,substrate scope,yields,and mechanistic insights across different methodologies.
作者
王艺皓
金海瑞
秦杰
赵亚婷
夏吾炯
WANG Yihao;JIN Hairui;QIN Jie;ZHAO Yating;XIA Wujiong(College of Chemical Engineering,Zhejiang University of Technology,Hangzhou 310032,China;College of Chemical and Material Engineering,Quzhou University,Quzhou 324000,China;School of Chemistry and Molecular Engineering,Nanjing Tech University,Nanjing 211816,China;School of Science,Harbin Institute of Technology(Shenzhen),Shenzhen 518055,China)
出处
《合成化学》
2025年第9期660-700,共41页
Chinese Journal of Synthetic Chemistry
基金
国家自然科学基金资助项目(21901141)
衢州市科技局资助项目(2024K139)。
