有机化学 ›› 2021, Vol. 41 ›› Issue (11): 4459-4466.DOI: 10.6023/cjoc202106035 上一篇    下一篇

研究论文

铜催化脂肪族环状叔胺的区域选择性C(sp3)—H磺酰亚胺化

苟铨a,*(), 谭秋健a, 陈乾琼a, 谭建红a, 王凯民c, 谢剑锋b,*()   

  1. a 长江师范学院化学化工学院 重庆 408100
    b 中国科学院大学重庆市人民医院 重庆 400013
    c 云南民族大学化学与环境学院 昆明 650500
  • 收稿日期:2021-06-21 修回日期:2021-07-17 发布日期:2021-07-26
  • 通讯作者: 苟铨, 谢剑锋
  • 基金资助:
    重庆市教育委员会研究(CXQT20026); 重庆市科学技术委员会基础研究与前沿探索(cstc2019jcyj-msxm1275); 涪陵区科学技术研究(FLKJ); 涪陵区科学技术研究(2019ABB2038); 重庆市教育委员会科学技术研究(KJQN202001403)

Copper-Catalyzed Regioselective C(sp3)—H Sulfonimidization of Aliphatic Cyclic Tertiary Amines

Quan Goua(), Qiujian Tana, Qianqiong Chena, Jianhong Tana, Kaimin Wangc, Jianfeng Xieb()   

  1. a School of Chemistry and Chemical Engineering, Yangtze Normal University, Chongqing 408100
    b Department of Chongqing General Hospital, University of Chinese Academy of Sciences, Chongqing 400013
    c School of Chemistry and Environment, Yunnan Minzu University, Chongqing 650500
  • Received:2021-06-21 Revised:2021-07-17 Published:2021-07-26
  • Contact: Quan Gou, Jianfeng Xie
  • Supported by:
    Chongqing Municipal Education Commission(CXQT20026); Basic Research and Frontier Exploration of Science and Technology Commission of Chongqing(cstc2019jcyj-msxm1275); Fuling District Science and Technology(FLKJ); Fuling District Science and Technology(2019ABB2038); Science and Technology Research Program of Chongqing Municipal Education Commission(KJQN202001403)

报道了一种简洁、高效的合成方法, 即铜催化的磺酰胺与脂肪族环状叔胺直接碳氢脱氢偶联, 实现高区域选择性地合成(E)-N-磺酰甲脒衍生物. 该反应条件简单, 无需使用腐蚀性酸或碱作为添加剂, 并兼容多种底物和官能团. 同时该方法能够实现克级反应和药物分子的后期功能修饰.

关键词: 铜催化, 脂肪族环状叔胺, 区域选择性, 磺酰甲脒

This paper reports a concise and efficient synthesis method, namely copper-catalyzed direct hydrocarbon dehydrogenation coupling of sulfonamides and aliphatic cyclic tertiary amines, to realize the highly regioselective synthesis of (E)-N-sulfonylformamidines. The reaction is accomplished without any corrosive acid or base as an additive. It tolerates a broad scope of substrates, good functional group compatibility, and generates exclusive (E)-stereoselectivity. Moreover, this utility of the protocol is successfully demonstrated in a late-stage functionalization of medicinally active molecules and gram-scale synthesis.

Key words: copper catalysis, aliphatic cyclic tertiary amines, regioselective, sulfonylformamidines