Electrochemical Allylic Hydrodefluorination Reaction Using Gaseous Ammonia as Hydrogen Source

doi:10.6023/cjoc202006071

Chinese Journal of Organic Chemistry ›› 2020, Vol. 40 ›› Issue (11): 3873-3880.DOI: 10.6023/cjoc202006071 Previous Articles Next Articles

Special Issue: 创刊四十周年专辑

以氨气为氢源的电化学烯丙位氢化脱氟反应研究

盛杰^a, 吴娜^a, 刘旭^a, 刘峰^a, 刘帅^a, 丁伟杰^a, 刘畅^a, 程旭^a,b

a 南京大学化学化工学院江苏省先进有机材料重点实验室化学与生物医学科学研究所南京 210023;
b 南开大学元素有机化学国家重点实验室天津 30071

收稿日期:2020-06-29 修回日期:2020-07-23 发布日期:2020-08-06
通讯作者: 程旭 E-mail:chengxu@nju.edu.cn
基金资助:
国家自然科学基金（No.22071105，22031008）、江苏省教育厅青蓝工程和国家重点研发计划（No.2019YFC0408303）资助项目.

Electrochemical Allylic Hydrodefluorination Reaction Using Gaseous Ammonia as Hydrogen Source

Sheng Jie^a, Wu Na^a, Liu Xu^a, Liu Feng^a, Liu Shuai^a, Ding Weijie^a, Liu Chang^a, Cheng Xu^a,b

a Institute of Chemical and Biomedical Science, Jiangsu Advanced Organic Material Laboratory, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023;
b State Key Laboratory of Elemento-organic Chemistry, Nankai University, Tianjin 300071

Received:2020-06-29 Revised:2020-07-23 Published:2020-08-06
Supported by:
Project supported by the National Natural Science Foundation of China (Nos. 22071105, 22031008), the QingLan Project of Jiangsu Education Department and the National Key Research and Development Program of China (No. 2019YFC0408303).

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Abstract

gem-Difluoroalkenes have wide applications in the drug designs and act as the synthon of molecules containing fluoride. The current researches on the electrochemical syntheses of gem-difluoroalkenes are limited to the silylation of enolated trifluoromethyl ketones. Herein, by using graphite felt as electrodes, the electrochemical allylic hydrodefluorination of α-trifluoromethyl cinnamates is realized using gaseous ammonia as hydrogen source, giving gem-difluorostyrenes in moderate to good yields. The usage of ammonia and graphite felt cathode is important to inhibit the cathodic hydrogen evolution, keeping the electron transfer from cathode to substrate with high selectivity. The cyclic voltammetry (CV) and square wave voltammetry (SWV) analyses support a stepwise electron transfer process to achieve the C—H bond formation and C—F bond cleavage.

Key words: electrochemistry, ammonia, C-F bond activation, graphite felt electrode

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Sheng Jie, Wu Na, Liu Xu, Liu Feng, Liu Shuai, Ding Weijie, Liu Chang, Cheng Xu. Electrochemical Allylic Hydrodefluorination Reaction Using Gaseous Ammonia as Hydrogen Source[J]. Chinese Journal of Organic Chemistry, 2020, 40(11): 3873-3880.

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以氨气为氢源的电化学烯丙位氢化脱氟反应研究

Electrochemical Allylic Hydrodefluorination Reaction Using Gaseous Ammonia as Hydrogen Source

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