Chinese Journal of Organic Chemistry ›› 2022, Vol. 42 ›› Issue (4): 1146-1162.DOI: 10.6023/cjoc202107062 Previous Articles     Next Articles


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

王玉斌a, 郭成b, 陶晟a, 刘纪昌a,c, 赵基钢a,c, 刘宁a,*(), 代斌a,*()   

  1. a 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
    b 浙江大学医学院 第二附属医院癌症研究所 杭州 310009
    c 华东理工大学化学工程学院 上海 200237
  • 收稿日期:2021-07-29 修回日期:2021-09-29 发布日期:2022-05-10
  • 通讯作者: 刘宁, 代斌
  • 基金资助:
    兵团中青年科技创新领军人才计划项目(2020CB027); 石河子市中青年科技创新领军人才计划项目(2019RC01); 石河子大学大型贵重仪器设备共享测试基金资助项目.

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

Yubin Wanga, Cheng Guob, Sheng Taoa, Jichang Liua,c, Jigang Zhaoa,c, Ning Liua(), Bin Daia()   

  1. a Key Laboratory for Green Processing of Chemical Engineering of Xinjiang Bingtuan, School of Chemistry and Chemical Engineering, Shihezi University, Shihezi, Xinjiang 832003
    b Cancer Institute, The Second Affiliated Hospital Zhejiang University School of Medicine, Hangzhou 310009
    c School of Chemical Engineering, East China University of Science and Technology, Shanghai 200237
  • Received:2021-07-29 Revised:2021-09-29 Published:2022-05-10
  • Contact: Ning Liu, Bin Dai
  • Supported by:
    Xinjiang Bingtuan Young and Middle-Aged Leading Scientists Program(2020CB027); Shihezi Young and Middle-Aged Leading Scientists Program(2019RC01); Open Sharing Fund for the Large-scale Instruments and Equipment of Shihezi University.

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 K2S2O8 as oxidants. By changing bases to NaHCO3, 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.

Key words: benzimidazolone, benzodiazepine, oxidant-induced, metal-free