Electroreductive Cross-Coupling of Trifluoromethyl Alkenes and Redox Active Esters for the Synthesis of Gem-Difluoroalkenes.

Abstract

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.