Chinese Journal of Organic Chemistry ›› 2021, Vol. 41 ›› Issue (8): 3223-3234.DOI: 10.6023/cjoc202103049 Previous Articles     Next Articles

Special Issue: 有机电合成虚拟专辑



高君青a, 翁信军b, 马聪b, 徐学涛a,*(), 方萍b,*(), 梅天胜b,*()   

  1. a 五邑大学生物科技与大健康学院 广东江门 529020
    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 分子合成卓越中心 上海 200032
  • 收稿日期:2021-03-26 修回日期:2021-04-26 发布日期:2021-05-14
  • 通讯作者: 徐学涛, 方萍, 梅天胜
  • 作者简介:
    † 共同第一作者
  • 基金资助:
    国家自然科学基金(21772222); 国家自然科学基金(21821002); 广东省教育厅基金(2017KSYS010); 广东省教育厅基金(2017KZDXM084); 广东省教育厅基金(2019KZDZX2003); 广东省教育厅基金(2019KZDXM035)

Electrochemical 2,2,6,6-tetramethylpiperidinyl-N-oxyl (TEMPO)-Mediated α-Cyanation and Phosphonylation of Cyclic Amines with Metal-Free Conditions

Junqing Gaoa, Xinjun Wengb, Cong Mab, Xuetao Xua(), Ping Fangb(), Tiansheng Meib()   

  1. a School of Biotechnology and Health Science, Wuyi University, Jiangmen, Guangdong 529020
    b Center for Excellence in Molecular Synthesis, State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032
  • Received:2021-03-26 Revised:2021-04-26 Published:2021-05-14
  • Contact: Xuetao Xu, Ping Fang, Tiansheng Mei
  • About author:
    † (These authors contributed equally to this work).
  • Supported by:
    National Natural Science Foundation of China(21772222); National Natural Science Foundation of China(21821002); Department of Education of Guangdong Province(2017KSYS010); Department of Education of Guangdong Province(2017KZDXM084); Department of Education of Guangdong Province(2019KZDZX2003); Department of Education of Guangdong Province(2019KZDXM035)

Metal-free electrochemical oxidation cyanation and phosphonylation reactions had been developed, in which 2,2,6,6-tetramethylpiperidinyl-N-oxyl (TEMPO) reduced the electrode potential of substrate and avoided over oxidation of some electron rich aromatic amines under electrochemical conditions. This protocol had good functional group compatibility, which made it to be a practical and efficient method to synthesize α-aminonitriles and α-amino phosphonates under mild conditions. Preliminary study indicated that the formation of the product was through the Shono oxidation of imine species.

Key words: electrochemistry, Shono oxidation, cyanation, phosphonylation