Institut de Chimie des Substances Naturelles, CNRS, UPR2301, Université Paris-Saclay, 1 Avenue de la Terrasse, 91198, Gif-sur-Yvette cedex, France.
Université Paris-Saclay, ENS Paris-Saclay, CNRS, PPSM, 91190, Gif-sur-Yvette, France.
Chemistry. 2022 Jan 10;28(2):e202103337. doi: 10.1002/chem.202103337. Epub 2021 Nov 16.
An electroreductive access to gem-difluoroalkenes has been developed through the decarboxylative/defluorinative coupling of N-hydroxyphtalimides esters and α-trifluoromethyl alkenes. The electrolysis is performed under very simple reaction conditions in an undivided cell using cheap carbon graphite electrodes. This metal-free transformation features broad scope with good to excellent yields. Tertiary, secondary as well as primary alkyl radicals could be easily introduced. α-aminoacids L-aspartic and L-glutamic acid-derived redox active esters were good reactive partners furnishing potentially relevant gem-difluoroalkenes. In addition, it has been demonstrated that our electrosynthetic approach toward the synthesis of gem-difluoroalkenes could use an easily prepared Kratitsky salt as alkyl radical precursor via a deaminative/defluorinative carbofunctionalization of trifluoromethylstyrene.
通过 N-羟邻苯二甲酰亚胺酯和α-三氟甲基烯烃的脱羧/脱氟偶联，开发了一种电还原方法来制备偕二氟烯烃。在非分隔电池中，使用廉价的碳石墨电极，在非常简单的反应条件下进行电解。这种无金属转化具有广泛的适用范围，产率良好至优秀。可以轻松引入叔、仲和伯烷基自由基。α-氨基酸 L-天冬氨酸和 L-谷氨酸衍生的氧化还原活性酯是很好的反应伙伴，可以提供潜在相关的偕二氟烯烃。此外，已经证明，我们通过电合成方法合成偕二氟烯烃，可以使用易于制备的 Kratitsky 盐作为烷基自由基前体，通过三氟甲基苯乙烯的脱氨/脱氟碳官能化反应来实现。
