铜催化二氟乙醇的芳基醚化反应及其机理研究

doi:10.6023/cjoc202003035

有机化学 ›› 2020, Vol. 40 ›› Issue (7): 2018-2025.DOI: 10.6023/cjoc202003035 上一篇下一篇

研究论文

铜催化二氟乙醇的芳基醚化反应及其机理研究

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

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 E-mail:zzjiang78@hznu.edu.cn;liwenxu@hznu.edu.cn
基金资助:
国家自然科学基金（Nos.21703051，21801056）和杭州市科技局（No.20180432B05）资助项目.

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

Huang Shuaishuai^a, Nie Yixue^a, Yang Jingjing^a, Zheng Zhanjiang^a, Cao Jian^a, Xu Zheng^a, Xu Liwen^a,b

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).

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摘要/Abstract

有机氟硅化合物是元素有机化学中最重要的高端产品种类之一，极具研究价值.开发了含二氟乙醇农药的新工艺技术，发展了一种条件温和和高效的铜催化二氟乙醇芳基醚化反应，通过大量的配体筛选和条件优化，建立了二氟乙醇和芳基溴或芳基碘的C—O偶联反应，简易合成出各种芳基取代的二氟乙基芳基醚.该反应以CuI为催化剂，在8-羟基喹啉和叔丁醇钾存在下顺利进行，具有广泛的底物适用性.ESI-MS分析证明，该催化过程可能存在三价铜催化机制，密度泛函理论（DFT）计算进一步表明该反应机理可能涉及三价铜的氧化加成、亲核取代及还原消除过程.

关键词: 乌尔曼反应, 铜催化, 含氟化合物, DFT计算, 8-羟基喹啉

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

引用此文

黄帅帅, 聂一雪, 杨晶晶, 郑战江, 曹建, 徐征, 徐利文. 铜催化二氟乙醇的芳基醚化反应及其机理研究[J]. 有机化学, 2020, 40(7): 2018-2025.

Huang Shuaishuai, Nie Yixue, Yang Jingjing, Zheng Zhanjiang, Cao Jian, Xu Zheng, Xu Liwen. Copper-Catalyzed Arylated Etherification of 2,2-Difluoroethanol and Its Mechanistic Study[J]. Chinese Journal of Organic Chemistry, 2020, 40(7): 2018-2025.

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铜催化二氟乙醇的芳基醚化反应及其机理研究

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

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