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 RFI and Al.