Anionic alkene-azide cycloaddition(AAAC) strategy toward electrosynthesis of multifunctionalized [60]fullerene derivatives and further applications  

通过负离子烯烃-叠氮环加成策略电化学合成多官能化富勒烯衍生物及其应用

作　　者：Xing-Xing Yan Chuang Niu Zheng-Chun Yin Wen-Qiang Lu Guan-Wu Wang 闫星星;牛闯;音正春;陆文强;王官武(Hefei National Research Center for Physical Sciences at the Microscale and Department of Chemistry,University of Science and Technology of China,Hefei 230026,China;State Key Laboratory of Applied Organic Chemistry,Lanzhou University,Lanzhou 730000,China)

机构地区：[1]Hefei National Research Center for Physical Sciences at the Microscale and Department of Chemistry,University of Science and Technology of China,Hefei 230026,China [2]State Key Laboratory of Applied Organic Chemistry,Lanzhou University,Lanzhou 730000,China

出　　处：《Science Bulletin》2022年第23期2406-2410,M0003,共6页科学通报（英文版）

基　　金：supported by the National Natural Science Foundation of China (22071231 and 21772189)。

摘　　要：It is a challenging task to control regioselective cycloaddition for polyolefins.Triazolines are a prominent class of heterocycles in organic synthesis and pharmaceutical chemistry.Among the numerous synthetic protocols for the formation of triazolines,the 1,3-dipolar cycloaddition of azides to neutral alkenes is an effective method[1].To the best of our knowledge,the ionic cycloaddition between azides and ionic alkenes remains unexplored to date.It has been found that Coobehaves likean electron-deficientalkene and that its[6,6]-bonds are C=C double bonds and dipolarophilic,which enable C_(60) to undergo various[2+3]cycloadditions[2].有机叠氮化合物与离子烯烃之间的离子环加成反应至今尚未研究.本文提出了前所未有的负离子烯烃-叠氮环加成(AAAC)策略,用于合成多功能化[60]富勒烯衍生物3.[60]富勒吲哚林二负离子12-与叠氮化合物2在室温下发生点击型反应,区域选择性地生成鹿角型产物3.它具有两个五元杂环链接在两个[5,6]-键上,并且两个氢位于两个杂环两侧,这是从未报道过的加成模式.产物3通过光化学反应意外地得到了四官能化衍生物4,而相应的热分解则产生了六官能化的开孔氮杂富勒烯衍生物5.目前负离子富勒烯化合物与叠氮化合物的点击反应为具有独特加成模式的多功能化富勒烯衍生物的区域选择性合成提供了一种新策略.后续的光化学和热转换反应出乎意料地脱氮重排得到了新颖的富勒烯衍生物,这也是现有方法无法获得的.此外,代表性的富勒烯产物作为修饰层被应用于钙钛矿太阳能电池器件中可有效提高光电转化效率.

关 键 词：富勒烯衍生物 叠氮化合物 区域选择性 环加成反应 电化学合成 光化学反应 点击反应 加成 

分 类 号：O621.3[理学—有机化学]