串联的铜、钯催化偶联-环化合成二芳胺基芴有机化学.pdfVIP

DOI: 10.6023/cjoc201503041 研究论文 有机化学 Chinese Journal of Organic Chemistry ARTICLE 串联的铜、钯催化偶联-环化合成二芳胺基芴 蔡良珍 蔺 卉 刘涛平 陶晓春* (华东理工大学化学与分子工程学院 上海 200237) 摘要 发展了一种由串联的铜、钯金属催化偶联-环化合成二芳胺基芴类衍生物的新方法. 取代的碘苯与甲基和溴原子 互为邻位的苯胺在铜催化下反应生成溴代甲基三苯胺, 然后与邻氯苯基硼酸在钯催化下发生 Suzuki 偶联反应, 最后在 3 NHC-Pd 催化下发生 C(sp )—H 键活化-环化反应. 方便地合成了 2 位, 尤其是 3 位取代的二芳胺基芴类化合物, 且均获 得了不错的收率. 所有化合物均通过了 1H NMR, 13C NMR, HRMS, IR, 紫外和荧光等手段的表征. 对其中两个具有代 表性的二芳胺基芴的结构运用二维核磁共振技术进行了解析. 关键词 二芳胺基芴; C—H 活化; 铜催化; 钯催化 Synthesis of Diarylaminofluorenes through Tandem Copper and Palladium Catalyzed Coupling-Cyclizing Reactions Cai, Liangzhen Lin, Hui Liu, Taoping Tao, Xiaochun* (School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai 200237) Abstract A convenient method of tandem copper and palladium catalyzed coupling-cyclizing reactions has been developed for the preparation of diarylaminofluorenes. Methylbromotriphenylamines prepared by the copper-catalyzed reaction of sub- stituted iodobenzenes and methylbromoanilines, coupled with chlorophenylboronic acid under palladium catalyst to obtain the chlorophenylmethyltriphenylamines (V). A series of diarylaminofluorenes can be generated in good yields through palladi- 3 um-catalyzed activation of benzylic C(sp )—H bond of compound V. It was found that the 2-diarylaminofluorenes or 3-diarylaminofluorenes could be efficiently got. These compounds were characterized by