铜催化苯甲酰胺与烷基偶氮试剂环化合成含α-取代季碳中心异喹啉二酮  

Copper-catalyzed Cyclization of Benamides and Alkyl Azo Compounds Leading to Isoquinolinediones Bearingα-Substituted Quaternary Carbon

作　　者：邓佑林[1] 唐石[1] 袁莉[1] 李增增[1] 王良能[1] 李立洋 黄桂秀[1] 刘盈盈[1] 吴伊婷 付丽[1] 

机构地区：[1]吉首大学化学化工学院,湖南吉首416000

出　　处：《应用化学》2017年第3期330-337,共8页Chinese Journal of Applied Chemistry

基　　金：国家自然基金资助项目(21462017);吉首大学研究生科研创新项目资助(JGY201636);吉首大学科技处研究生科研项目(15JDY001);湖南省研究生培养创新基地(2014KFXM06)~~

摘　　要：发展了一种苯甲酰胺自由基自由基环化制备α-官能化叔烷基取代的异喹啉二酮的新反应。此环化反应以偶氮试剂为α-取代叔烷基自由基源物质,利用碘化亚铜/空气体系催化N-烷基-N-甲基丙烯酰基苯甲酰胺发生环化,经过串联自由基加成/环化/碳-碳键形成过程,一步构建了三重碳-碳键,以41%~71%的产率合成了一系列异喹啉二酮及其衍生物。特别值得提出得是,此研究发展了一种新型α-官能叔烷基自由基源物质,发现了一种同时引入两个α-官能叔烷基片段的串联新反应。反应底物适应范围广,反应高效,催化体系廉价实用,为具有潜在药用价值的含α-取代季碳中心的异喹啉二酮及衍生物的合成提供了一条廉价、简单、快捷的新途径。A radical cyclization reaction of benzamides toward isoquinolinedione bearing a-substituted quaternary carbon was developed. Using alkyl azo compounds as tertiary radical sources, N-alkyl-N- methacryloylbenzamides underwent cascade radical addition/cyclization/C-C bond formation in of Cu catalyst and air, and constructed triple-fold carbon-carbon bonds in a single step, leading the presence to a series of isoquinolinediones in 41% to 71% yield. Notably, this work discovered a new type of radical precursor to or-functional tertiary radical and a protocol to incorporate two or-functional tertiary alkyl moieties. The broad substrate scope and high efficiency allow this method a cheap, simple and rapid catalytic synthetic entry to pharmaceutically interesting isoquinolindiones.

关 键 词：异喹啉二酮 苯甲酰胺 串联环化 铜催化 烷基偶氮试剂 

分 类 号：O664[理学—分析化学]