微波辅助下铑催化二芳基膦酰胺与炔烃的C—H活化/环化反应  

Microwave Assisted Rhodium-catalyzed C—H Activation/cyclization of Diaryl Phosphoramides and Alkynes

作　　者：周春妮 郑子昂 彭望明[1] 王洪波 张玉敏[1] 王亮[1] 肖标[1] ZHOU Chunni;ZHENG Ziang;PENG Wangming;WANG Hongbo;ZHANG Yumin;WANG Liang;XIAO Biao(Key Laboratory of Optoelectronic Chemical Materials and Devices,Ministry of Education,School of Chemical and Environmental Engineering,Jianghan University,Wuhan 430056,China)

机构地区：[1]江汉大学化学与环境工程学院,光电化学材料与器件教育部重点实验室,武汉430056

出　　处：《高等学校化学学报》2020年第4期726-734,共9页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号:21302064);湖北省自然科学基金(批准号:2017CFB690,2019CFB198);湖北省高等学校优秀中青年科技创新团队计划项目(批准号:T201726)资助.

摘　　要：研究了微波条件下[RhCp^*Cl2]2(Cp^*:五甲基环戊二烯基)催化二芳基膦酰胺与炔烃的C-H活化/环化反应,以中等到较好的收率获得了一系列具有环状结构的含氟膦酰胺衍生物.通过考察溶剂、温度、时间以及碱等因素,筛选了最佳反应条件.对该催化体系进行放大量实验,也获得了良好的结果.在实验基础上,推测了可能的反应机理,并将此方法应用于一种新型含氟代环状膦酰胺二胺单体的制备.A microwave assisted rhodium-catalyzed C—H activation/cyclization of diaryl phosphoramides and alkynes has been developed,and a series of cyclic phosphoramides bearing five fluoro groups could be obtained in moderate to good yields.The optimized reaction conditions were established by examination of solvents,temperature,reaction time and bases.This reaction system was also feasible in a gram-scale reaction without significant decrease in the product yields,and a possible reaction mechanism was then proposed.Moreover,this methology was successfully applied to the synthesis of the novel diamine with the core of fluorine-containing substituted cyclic phosphoramide.

关 键 词：微波 [RhCp^*Cl2]2 C—H活化/环化反应 二芳基膦酰胺 

分 类 号：O626.1[理学—有机化学]