钯催化惰性碳-氢键胺化反应研究进展  

Recent advances on palladium-catalyzed C—H amination

作　　者：江梦雪 杨旭 周涛 史炳锋[2] JIANG Meng-xue;YANG Xu;ZHOU Tao;SHI Bing-feng(School of Biotechnology and Health Sciences,Wuyi University,Jiangmen 529020,China;Department of Chemistry,Zhejiang University,Hangzhou 310027,China)

机构地区：[1]五邑大学生物科技与大健康学院,广东江门529020 [2]浙江大学化学系,浙江杭州310027

出　　处：《分子科学学报》2021年第2期108-123,共16页Journal of Molecular Science

基　　金：国家自然科学基金资助项目(21801223)。

摘　　要：胺化反应是有机化学中最重要的反应之一,近年来,过渡金属催化的碳-氢键胺化反应已经成为合成有机胺化物的重要方法.本文综述了钯催化碳-氢键胺化反应的研究进展,按照底物类型和所活化碳-氢键的类型进行分类,并对该领域目前存在的局限性和未来发展进行了总结和展望.Nitrogen-containing molecules are ubiquitous in natural products,pharmaceuticals,pesticides and functional materials.The importance of such molecules has motivated many synthetic chemists to develop efficient and mild amination reactions.The directly transformation of ubiquitous C-H bonds into valuable C-N bonds is a highly promising approach to access N-functionalized molecules.In the last few decades,transition metal-catalyzed C-H amination have witnessed tremendous progress and has been recognized as one of the most efficient and straightforward strategies.To date,apart from the well-established nitrene insertion strategy,chelation assisted C-H amination reactions via metal insertion have been achieved by various metal catalysts,including Pd,Rh,Ru,Ir,Co,Cu,Ni,and Fe,etc.Palladium was one of the most outstanding catalysts in both C(sp2)-H and C(sp3)-H amination,due to its multiple catalytic cycles.In this review,recent advances on palladium-catalyzed C-H amination reactions enabled by a wide range of directing groups are summarized.Examples of palladium-catalyzed Catellani-type amination assisted by norbornene will not be covered.Initial discoveries,the evolution of amination reagents,mechanistic studies and the synthesis of different nitrogen-containing skeleton are the focus of this review.For clarification,C-H amination reactions are categorized first on the C(sp2)-H and C(sp3)-H bond activation in this review,and they are further subclassified into inter-and intramolecular reactions based on the type of substrates that used.With the development of various directing groups and amination reagents,Pd-catalyzed C-H amination has offered a brand new opportunity for the design and synthesis of nitrogen-containing functional molecules.Nevertheless,there are still some challenging problems remain to be solved in this cutting-edge field:(1)most of the C(sp2)-H amination of aryls are focused on the ortho-position of the directing group.More convenient methods to achieve meta-selective and para-selective C-H amination

关 键 词：钯 碳-氢键活化 胺化 酰胺化 

分 类 号：O621[理学—有机化学]