Addition of poZyfZuoroaZkyZ halides to alkynes and alkenes bearing a variety of substituents is effected by the cataZysis of iron, cobalt and rutheniwn carbonyl complexes to give the corresponding adducts in good to excellent yieZds under miZd conditions. Polyfluoroalkylation of carbon-carbon multiple bonds is one of the most important and general methods for the industrial as well as laboratory synthesis of a variety of organofluorine compounds containing polyfluoroalkyl groups. 2 It has been shown that the addition of polyfluoroalkyl iodides to alkynes or alkenes is effected by photolysis,3 pyrolysis,4 electrolysis,5 free radical initiators6 or CuI-ethanolamine catalyst.' However, these conventional methods do not necessarily guarantee satisfactory yields, and are sometimes hampered by side reactions. C8F,7CH=C(I)SiMe3 + CO + EtOH PdC12(PPh3+ Et3N/benzene > C8F,7CH=CHCOOEt 3b 10 (61 %) -C3F7CH=C(I)CH2CH20H + CO PdC12(PPh3&, K2C03/CH3CN c C3F7CH 9 0 3h 0 (4) (5) 11 (90 %) -Further studies on the expansion and application of the present reaction are currently underway.