有机化学 ›› 2019, Vol. 39 ›› Issue (10): 2821-2828.DOI: 10.6023/cjoc201904058 上一篇    下一篇

研究论文

Cu(0)/Selectfluor体系催化的邻芳基磺酰亚胺的串联环化/芳构化反应:一种简便合成6H-菲啶的方法

郑立孟, 施冬冬, 鲍汉扬, 刘运奎*()   

  1. 浙江工业大学化学工程学院 绿色化学与技术国家重点实验室培育基地 杭州 310014
  • 收稿日期:2019-04-24 修回日期:2019-05-26 出版日期:2019-10-25 发布日期:2019-06-12
  • 通讯作者: 刘运奎 E-mail:ykuiliu@zjut.edu.cn
  • 基金资助:
    国家自然科学基金(21772176);国家自然科学基金(21372201);浙江工业大学“省重中之重一级学科”开放基金资助项目

Copper(0)/Selectfluor System-Catalyzed Tandem Annulation/Aromatization of o-Aryl Benzenesulfonylimides:A Facile Synthesis of 6H-Phenanthridines

Zheng Limeng, Shi Dongdong, Bao Hanyang, Liu Yunkui*()   

  1. State Key Laboratory Breeding Base of Green Chemistry-Synthesis Technology, College of Chemical Engineering,Zhejiang University of Technology, Hangzhou 310014
  • Received:2019-04-24 Revised:2019-05-26 Online:2019-10-25 Published:2019-06-12
  • Contact: Liu Yunkui E-mail:ykuiliu@zjut.edu.cn
  • Supported by:
    Project supported by the National Natural Science Foundation of China(21772176);Project supported by the National Natural Science Foundation of China(21372201);The Opening Foundation of Zhejiang Key Course of Chemical Engineering and Technology, Zhejiang University of Technology

发展了Cu(0)/Selectfluor体系催化的邻芳基磺酰亚胺的串联环化/芳构化反应, 于温和的反应条件下以中等到良好的产率简便、高效地构建了一系列6H-菲啶类化合物. 机理研究表明, 反应的关键步骤经历了由Cu(0)/Selectfluor体系现场原位产生XCuOH (X=F, BF4)物种, 进而诱导对C=N键的羟铜化反应和分子内C—H键胺化反应, 从而合成了6H-菲啶类化合物.

关键词: 铜催化, Selectfluor, 6H-菲啶, 环化反应, C—H键胺化

A facile and efficient method for the synthesis of 6H-phenanthridines has been successfully developed involving a copper(0)/Selectfluor system-catalyzed tandem annulation/aromatization of o-aryl benzenesulfonylimides. A variety of substituted 6H-phenanthridines were synthesized in moderate to good yields under mild reaction conditions. Mechanistic experiments revealed that the reaction might involve an oxycupration of C=N bond followed by an intramolecular C—H bond amination as the key steps triggered by an in situ generated copper species XCuOH (X=F or BF4) from the Cu(0)/Selectfluor system.

Key words: copper catalysis, Selectfluor, 6H-phenanthridine, annulation reaction, C—H bond amination