Reaction of Perfluoroalkyl Iodides with Electron Donor Nucleophiles. Addition of Perfluoroalkyl Iodides to Olefins Initiated by Electron Transfer

Article abstract of DOI:10.1021/jo00218a006

The radical chain addition of primary and secondary perfluoroalkyl iodides to olefins is initiated by sodium arene- and alkanesulfinates.The process occurs at room temperature and is favored by the use of dipolar aprotic solvents.The reaction of perfluorooctyl iodide with sodium p-toluenesulfinate in the absence of olefin requires higher temperatures and gives only 1-H-perfluorooctane; no anion-perfluoroalkyl radical coupling products were detected.Reaction of perfluorooctyl iodide with the sodium salt of diethyl methylmalonate also gives no coupling product; only 1-H-perfluorooctane and a dimer of the malonate anion are produced.These results are compared with the reaction of perfluoroalkyl iodides with nitronate and thiolate anions where formation of S_RN1 substitution products was observed.