碱性调控的选择性:通过N-烷基-N-(2-(吡啶-2-基氨基)苯基)甲酰胺合成苯并咪唑酮和苯二氮䓬类化合物  

Basicity-Tuned Selectivity:Synthesis of Benzimidazolone and Benzodiazepine from N-Alkyl-N-(2-(pyridin-2-ylamino)-phenyl)formamides

作　　者：王玉斌 郭成 陶晟 刘纪昌 赵基钢[1,3] 刘宁 代斌[1] Wang Yubin;Guo Cheng;Tao Sheng;Liu Jichang;Zhao Jigang;Liu Ning;Dai Bin(Key Laboratory for Green Processing of Chemical Engineering of Xinjiang Bingtuan,School of Chemistry and Chemical Engineering,Shihezi University,Shihezi,Xinjiang 832003;Cancer Institute,The Second Affiliated Hospital Zhejiang University School of Medicine,Hangzhou 310009;School of Chemical Engineering,East China University of Science and Technology,Shanghai 200237)

机构地区：[1]石河子大学化学化工学院新疆兵团绿色化工过程重点实验室,新疆石河子832003 [2]浙江大学医学院第二附属医院癌症研究所,杭州310009 [3]华东理工大学化学工程学院,上海200237

出　　处：《有机化学》2022年第4期1146-1162,共17页Chinese Journal of Organic Chemistry

基　　金：兵团中青年科技创新领军人才计划项目(No.2020CB027);石河子市中青年科技创新领军人才计划项目(No.2019RC01);石河子大学大型贵重仪器设备共享测试基金资助项目.

摘　　要：发展了一种碱控制选择性合成苯并咪唑酮和吡啶并苯二氮䓬衍生物的方法.该方法以N-烷基-N-(2-(吡啶-2-基氨基)苯基)甲酰胺类化合物为原料,以K_(2)S_(2)O_(8)为氧化剂,当选用NaOAc为碱时,高选择性地得到了一系列苯并咪唑酮衍生物;当选用NaHCO_(3)为碱时,得到了一系列吡啶并苯二氮䓬衍生物.通过自由基捕捉实验的研究,提出了相应可能的反应机理.苯二氮䓬的克级放大实验和官能化衍生化实验说明该方法具有一定应用前景.A base-controlled strategy for the selective preparation of benzimidazolone and pyrido-benzodiazepine derivatives was developed.The N-alkyl-N-(2-(pyridin-2-ylamino)phenyl)formamides underwent selective coupling to synthesize a series of benzimidazolones when NaOAc was used as bases and employed K_(2)S_(2)O_(8) as oxidants.By changing bases to NaHCO_(3),a series of benzodiazepines was obtained.The possible reaction mechanism was proposed based on the radical-trapping experiments.The applicability of this protocol is demonstrated by scale-up experiments and the functionalization of benzodiazepine products.

关 键 词：苯并咪唑酮 苯二氮䓬 氧化剂诱导 无金属 

分 类 号：O626[理学—有机化学]