Reductive alkylation of perfluorocarboxylic acid esters with CCl3F or CCl4 and synthesis of higher linear perfluoroketones

Barbier-type reductive alkylation of perfluorocarboxylic acid esters (I) with CFCl₃ and activated Al was successfully performed to give α,α-dichloroperfluoroketones (II). A similar reaction of CF₃COOEt with CCl₄ and Al provided a convenient synthesis of CF₃COCCl₃. Ketones (II) were fluorinated further with SbF₅ to form higher linear perfluoroketones (IX). An alternative approach to the synthesis of ketones (IX) was proposed by reductive perfluoroalkylation of esters (I) under the action of R_FI and Al.