双功能CuX_(2)参与的芳基-7-氮杂吲哚邻位C-H键的卤化反应  

Difunctional CuX_(2)-Catalyzed Ortho-position C-H Halogenation of Aryl-7-azaindoles

作　　者：周鲜颖 张媛媛 刘珊珊 ZHOU Xianying;ZHANG Yuanyuan;LIU Shanshan(College of Chemistry and Chemical Engineering,Shaanxi University of Science&Technology,Xi’an 710021,China)

机构地区：[1]陕西科技大学化学与化工学院,陕西西安710021

出　　处：《广州化学》2023年第4期57-60,共4页Guangzhou Chemistry

摘　　要：开发了一种双功能铜参与催化芳基-7-氮杂吲哚的芳基卤化反应,该方法以N-苯基-7-氮杂吲哚类化合物为底物,CuX_(2)既为卤素源,又可以作为C-H键活化试剂,在无外加催化剂下,通过7-氮杂吲哚的导向作用选择性地发生芳环的亲电卤代反应。经过一系列条件筛选之后得到最佳反应条件为:CuCl_(2)(0.65eq)为催化剂,DMAP(0.25 eq)为配体,苯甲酸(1.2 eq)为添加剂,氯苯为溶剂,于120℃下反应24小时,产率最高达到95%。除7-氮杂吲哚导向基团外,还成功兼容了吡啶、喹啉等导向基团,该反应可应用于较多的底物范围。A difunctional copper-catalyzed aryl halogenation reaction of aryl-7-azaindole was developed.In this method,N-phenyl-7-azaindole compounds were used as substrates,and CuX_(2) was used as both halogen source and C-H bond activating reagent.In the absence of additional catalyst,electrophilic halogenation of aromatic rings was selectively carried out through the guidance of 7-azaindole.After a series of conditions screening,the optimum reaction conditions were as follows:CuCl_(2)(0.65 eq)as catalyst,DMAP(0.25 eq)as ligand,benzoic acid(1.2 eq)as additive and chlorobenzene as solvent,and the reaction temperature was 120℃ for 24 hours,with the highest yield of 95%.In addition to the 7-azaindole guiding group,it is also successfully compatible with pyridine,quinoline and other guiding groups,which has a wide range of substrates.

关 键 词：双功能 铜催化 7-氮杂吲哚 卤化 C-H键活化 自催化剂 

分 类 号：O621.3[理学—有机化学]