Chinese Journal of Organic Chemistry ›› 2022, Vol. 42 ›› Issue (1): 147-159.DOI: 10.6023/cjoc202108006 Previous Articles     Next Articles

ARTICLES

镍促进电化学还原交叉偶联合成偕二氟烯烃

常哲, 王佳鑫, 陆熹*(), 傅尧*()   

  1. 中国科学技术大学应用化学系 合肥 230026
  • 收稿日期:2021-08-06 修回日期:2021-09-05 发布日期:2021-09-14
  • 通讯作者: 陆熹, 傅尧
  • 基金资助:
    国家自然科学基金(21732006); 国家自然科学基金(51821006); 国家自然科学基金(51961135104); 中国科学技术大学双一流研究基金(YD3530002002)

Synthesis of gem-Difluoroalkenes through Nickel-Promoted Electrochemical Reductive Cross-Coupling

Zhe Chang, Jiaxin Wang, Xi Lu(), Yao Fu()   

  1. Department of Applied Chemistry, University of Science and Technology of China, Hefei 230026
  • Received:2021-08-06 Revised:2021-09-05 Published:2021-09-14
  • Contact: Xi Lu, Yao Fu
  • Supported by:
    National Natural Science Foundation of China(21732006); National Natural Science Foundation of China(51821006); National Natural Science Foundation of China(51961135104); Research Funds of the Double First-Class Initiative of University of Science and Technology of China(YD3530002002)

gem-Difluoroalkenes are important fluorine-containing compounds with structural superiority in organic synthetic chemistry and medicinal chemistry. For instance, the gem-difluoroethylene moiety could be converted to monofluoroalkenyl, difluoroalkyl, trifluoromethyl moiety, and many other fluorine-containing structures conveniently. The gem-difluoroethylene moiety is also an ideal carbonyl group bioisostere and has already been widely used in drug design. Herein, a nickel-promoted electrochemical reductive cross-coupling to access functionalized and substituted gem-difluoroalkenes is reported. This reaction enables the combination of allylic defluorination of trifluoromethyl alkenes and decarboxylation of redox-active esters or dehalogenation of alkyl halides under mild electrochemical reduction conditions and in an undivided cell, therefore obviates the use of stoichiometric amount metal powder or organic reductants. Furthermore, this reaction provides efficient access to biologically interesting molecules containing gem-difluoroethylene moiety.

Key words: gem-difluoroalkene, trifluoromethyl alkene, redox-active ester, alkyl halide, reductive cross-coupling, electrochemistry