摘要/Abstract

含氮化合物广泛存在于天然产物、药物分子和合成中间体中, 因此在有机化合物中引入含氮官能团具有重要的意义. 尽管过渡金属催化的C—N偶联反应为含氮化合物的构建提供了一种应用广泛的策略, 然而需要多步预官能团化的反应底物. 近年来, 过渡金属催化的碳氢键胺化反应为碳-氮键的构建提供了更具原子经济性和步骤经济性的全新策略. 与钯、铑等贵金属相比, 铜、钴、镍等廉价金属由于地球储量丰富, 更为廉价易得, 且往往具有独特的催化活性, 而受到广泛关注. 按照廉价金属、碳氢键和胺化试剂的类型进行分类, 综述了近年来铜、钴、镍催化的导向基辅助的碳氢键胺化反应研究进展, 着重探讨了各种胺化试剂及其应用, 并对目前该领域的局限性和发展趋势进行了分析和展望.
关键词: 廉价金属, 碳氢键活化, 胺化, 导向基, 铜, 钴, 镍
Nitrogen-containing organic compounds are ubiquitous in natural products, drug molecules and organic intermediates. Therefore, the introduction of nitrogenous functional groups into organic compounds is of great significance. Despite transition metal-catalyzed C—N coupling reaction provided an effcient strategy to access these ntrogen-containing compounds, extra steps are generally required to obtain the pre-functionalized starting materials. Recently, transition metal-catalyzed C—H amination has emerged as a more atom- and step-economical strategy to construct C—N bonds. Compared to the noble metals (e.g. palladium and rhodium), base metal catalysts, such as copper, cobalt and nickel, have attracted dramatic attentions, due to their earth abundance, cost effectiveness, and unique catalytic activities. Herein, the recent advances in copper-, cobalt- and nickel-catalyzed C—H amination reactions assisted by directing groups were summmarized according to the types of base metals, C—H bonds, and amination reagents with an emphasis on the discussion of various amination reagents and their application. Finally, the limitations and development trend of this research field are analyzed and prospected.
Key words: base metal, C—H activation, amination, directing group, copper, cobalt, nickel


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