A simple, mild and efficient approach for the fluoroalkylation of alkenes and alkynes using 2-bromophenol as a catalyst is presented.

Atom transfer radical addition and Heck-type reaction between alkenes and ethyl iododifluoroacetate by using organophosphine compounds as catalysts have been developed. The reaction proceeds under mild reaction conditions with excellent functional group tolerance and high chemo-and regioselectivities. Mechanistic study indicates that the reaction might be initiated via noncovalent interactions between an organophosphine catalyst and a carbon−iodine bond.