钯催化的氯二氟乙基高价碘试剂对于乙酰苯胺C—H键的氯二氟乙基化反应研究  

Pd-Catalyzed Chlorodifluoroethylation Reaction of C—H Bond of Acetanilides with Chlorodifluoroethyl Iodonium Reagents

作　　者：曹成瑶 牛亚茹 蒋昀辰 曲红梅[2] 陈超[1,3] Cao Chengyao Kimmy;Niu Yaru;Jiang Yunchen;Qu Hongmei;Chen Chao(Key Laboratory of Bioorganic Phosphorus Chemistry and Chemical Biology(Ministry of Education),Department of Chemistry,Tsinghua University,Beijing 100084;Key Laboratory of Systems Bioengineering,Ministry of Education,Department of Pharmaceutical Engineering,School of Chemical Engineering and Technology,Tianjin University,Tianjin 300350;State Key Laboratory of Elemento-Organic Chemistry,Nankai University,Tianjin 300071)

机构地区：[1]清华大学化学系生物有机磷化学与化学生物学教育部重点实验室,北京100084 [2]天津大学化工学院制药工程系系统生物工程教育部重点实验室,天津300350 [3]南开大学元素有机化学国家重点实验室,天津300071

出　　处：《有机化学》2022年第7期2098-2105,共8页Chinese Journal of Organic Chemistry

基　　金：国家重点研发项目(No.2016YFB0401400);国家自然科学基金(Nos.22071129,21871158,21672120);霍英东基金(No.151014)资助项目.

摘　　要：二氟乙基化合物在生物医药和材料领域有着广泛的应用,合成二氟乙基的化合物有着重要意义,在此报道了一种钯催化的乙酰苯胺邻位氯二氟乙基化的反应,该反应利用氯二氟乙基高价碘试剂(CDFI)作为CH_(2)CF_(2)Cl的来源.进一步研究发现,有机碱1,8-二氮杂二环[5.4.0]十一碳-7-烯(DBU)加入到反应体系中,可以通过消除反应制备乙酰苯胺邻位偕二氟乙烯基化产物.Difluoroethyl products have a wide range of applications in the fields of biomedicine and materials,and it is important to develop new method to synthesize difluoroethyl compounds.Herein,a palladium-catalyzed chlorodifluoroethylation was disclosed via ortho-C—H activation of acetanilide,using chlorodifluoroethyl(mesityl)hypervalent iodine reagent as the source of CH_(2)CF_(2)Cl.Moreover,adding organic base 1,8-diazabicyclo[5.4.0]undec-7-ene(DBU)to the above system,the difluorovinylated acetanilide products were obtained via an elimination reaction.

关 键 词：C—H活化 钯催化 乙酰苯胺 碘鎓盐 氯二氟乙基化 二氟乙烯基化 

分 类 号：O621.251[理学—有机化学]