Redox-Initiated Per(poly)fluoroalkylation of Olefins by Per(poly)fluoroalkyl Chlorides

Article abstract of DOI:10.1021/jo00022a025

The per(poly)fluoroalkylation of olefins by per(poly)fluoroalkyl chlorides, initiated by ammonium persulfate/sodium formate ((NH4)2S2O8/HCO2Na), is described.The reaction proceeds smoothly in polar aprotic solvents. The presence of functional groups like sodium carboxylate or sulfonate in the polyfluoroalkyl chloride appear to facilitate the reaction.The reaction appears to be initiated by a single-electron transfer, represents the firat example of the reactivity of per(poly)fluoroalkyl chlorides, and also demonstrates their use as per(poly)fluoroalkylating agents.For α-chloro-ω-iodoperfluoroalkanes only the carbon-iodine bond is cleaved during the reaction.An explantation for the apparent stability of the carbon-chlorine bond in such compounds is given.