Chinese Journal of Organic Chemistry ›› 2020, Vol. 40 ›› Issue (7): 2018-2025.DOI: 10.6023/cjoc202003035 Previous Articles     Next Articles


黄帅帅a, 聂一雪a, 杨晶晶a, 郑战江a, 曹建a, 徐征a, 徐利文a,b   

  1. a 杭州师范大学 有机硅化学及材料技术教育部重点实验室 杭州 311121;
    b 杭州师范大学 氟硅精细化学品与材料制造协同创新中心 杭州 311121
  • 收稿日期:2020-03-14 修回日期:2020-04-17 发布日期:2020-04-23
  • 通讯作者: 郑战江, 徐利文;
  • 基金资助:

Copper-Catalyzed Arylated Etherification of 2,2-Difluoroethanol and Its Mechanistic Study

Huang Shuaishuaia, Nie Yixuea, Yang Jingjinga, Zheng Zhanjianga, Cao Jiana, Xu Zhenga, Xu Liwena,b   

  1. a Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Hangzhou Normal University, Hangzhou 311121;
    b Collaborative Innovation Center for Fluorosilicone-based Fine Chemicals and Materials, Hangzhou Normal University, Hangzhou 311121
  • Received:2020-03-14 Revised:2020-04-17 Published:2020-04-23
  • Supported by:
    Project supported by the National Natural Science Foundation of China (Nos. 21703051, 21801056) and the Hangzhou Science and Technology Bureau of China (No. 20180432B05).

Both organofluorine and organosilicon compounds are one of the most important types of high-tech product in elementorganic chemistry, and have been received much attetions in the past decades. Considering the imporatance of difluoroethanol moeity in pesticides, the development of a mild and efficient copper-catalyzed arylated etherification reaction of difluoroethanol is highly desirable. Herein, a mild and efficient method for the preparation of difluoroethyl aryl ethers was developed by the copper-catalyzed Ullmann-type arylated etherification reaction of aryl bromides or iodides with 2,2-difluoroethanol. This reaction proceeds smoothly in the presence of CuI and 8-hydroxyquinoline/t-BuOK, and has a broad substrate scope. ESI-MS analysis supported the existence of LCu(Ⅲ)Ar(OR) species during this catalytic reaction. Further density functional theory (DFT) calculations suggest a proposed mechanism of arylated etherification reaction involving oxidative addition, followed by nucleophile substitution and reductive elimination would be rational.

Key words: Ullmann reaction, Cu-catalyzed, fluorinated compound, DFT calculation, 8-hydroxyquinoline