Abstract An efficient method for the preparation of the synthetically attractive perfluoroalkyl ketones through the reaction of readily available alkenoates, alkynoates, or regular carboxylic esters with perfluoroalkyl Grignard reagents at–70 to–60 C in diethyl ether with moderate to good yields was developed. The reaction stopped at the ketone stage, with no further reaction to form the tertiary alcohols being observed. DFT calculations confirmed ...