有机化学 ›› 2024, Vol. 44 ›› Issue (3): 940-950.DOI: 10.6023/cjoc202401002 上一篇    下一篇

研究论文

电化学促进2,2,6,6-四甲基哌啶氧化物(TEMPO)介导的甘氨酸衍生物氧化脱氢Povarov/串联反应

李章健a,b, 王振华b, 郭剑峰b, 方萍b, 马聪b,*(), 刘润华b,c,*(), 梅天胜b,c,*()   

  1. a 四川师范大学化学与材料科学学院 成都 610068
    b 中国科学院上海有机化学研究所 金属有机化学国家重点实验室 中国科学院大学 上海 200032
    c 中国科学院上海有机化学研究所 宁波中科新材料创制中心 浙江宁波 315800
  • 收稿日期:2024-01-04 修回日期:2024-02-28 发布日期:2024-04-02
  • 基金资助:
    中国科学院战略性先导科技专项(XDB0610000); 国家重点研发项目(2021YFA1500100); 国家自然科学基金(21821002); 国家自然科学基金(91956112); 国家自然科学基金(22101294); 上海市科学技术委员会(21ZR1476500); 上海市科学技术委员会(20XD1425100); 宁波市自然科学基金(2023J035)

Electrochemistry-Enabled 2,2,6,6-Tetramethylpiperidoxyl (TEMPO)-Mediated Oxidative Dehydrogenation Povarov/Tandem Reactions of Glycine Derivatives

Zhang-Jian Lia,b, Zhen-Hua Wangb, Jian-Feng Guob, Ping Fangb, Cong Mab(), Run-Hua Liub,c(), Tian-Sheng Meib,c()   

  1. a College of Chemistry and Materials, Sichuan Normal University, Chengdu 610068
    b State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, Shanghai 200032
    c Ningbo Zhongke Creation Center of New Materials, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Ningbo, Zhejiang 315800
  • Received:2024-01-04 Revised:2024-02-28 Published:2024-04-02
  • Contact: *E-mail: mei7900@sioc.ac.cn; macong2016@sioc.ac.cn; liurh@mail.sioc.ac.cn
  • Supported by:
    Strategic Priority Research Program of the Chinese Academy of Sciences(XDB0610000); National Key R&D Program of China(2021YFA1500100); National Natural Science Foundation of China(21821002); National Natural Science Foundation of China(91956112); National Natural Science Foundation of China(22101294); Science and Technology Commission of Shanghai Municipality of Shanghai(21ZR1476500); Science and Technology Commission of Shanghai Municipality of Shanghai(20XD1425100); Natural Science Foundation of Ningbo(2023J035)

研究了电化学氧化甘氨酸衍生物与烯烃之间的氧化脱氢Povarov/串联反应, 其中氮氧自由基2,2,6,6-四甲基哌啶氧化物(TEMPO)作为媒介降低了电化学反应的电位, 避免了某些富电子的芳胺在较高电位下的过氧化. 它为甘氨酸衍生物的氮-α位官能团化提供了潜在的途径, 并通过Shono氧化与Povarov反应的结合, 开发了一种在温和条件下高产率合成喹啉衍生物的有效方法.

关键词: 电化学, 2,2,6,6-四甲基哌啶氧化物(TEMPO), Povarov反应, Shono氧化

The oxidative dehydrogenation Povarov/tandem reaction between electrochemically oxidized glycine derivatives and olefins was investigated. Specifically, a nitrogen oxide radical 2,2,6,6-tetramethylpiperidoxyl (TEMPO) was used as a redox mediator to reduce the potential of the electrochemical reaction and avoid over-oxidation of electron-rich aromatic amines at higher potentials. The reaction provides a potential pathway for the nitrogen-α functionalization of glycine derivatives. Further, the reaction represents an efficient method for synthesizing quinoline derivatives under mild conditions to achieve high yields through a combination of Shono oxidation and Povarov reactions.

Key words: electrochemistry, 2,2,6,6-tetramethylpiperidoxyl (TEMPO), Povarov reaction, Shono oxidation