Abstract Pivaloylpyruvic acid is an efficient reagent for preparative acylation of amines. A method for the synthesis of substituted pivaloylpyruvamides with domination of (Z)-β-keto- enol tautomer is proposed. The structure of pivaloylpyruvic acid and its amides, as well as the specific features of the reaction of pivaloylpyruvic acid with amines, are discussed.