A variety of esters react with perfluoroalkyllithiums in situ generated from perfluoroalkyl iodides and methyllithium to give perfluoroalkyl ketones in good yields. Perfluoroalkyllithiums add to α, β-unsaturated esters only in the 1, 2-addition mode even in the presence of copper salt. Exception was observed in the reaction with maleates where perfluoroalkylated succinic esters and normal 1, 2-addition products are obtained in ...