Radical Iodination of C-H Bond

Alexander Artaryan, Schulich Faculty of Chemistry, Technion – Israel Institute of Technology, Haifa, Israel
Kseniya Kulbitski, Schulich Faculty of Chemistry, Technion – Israel Institute of Technology, Haifa, Israel
Gennady Nisnevich, Schulich Faculty of Chemistry, Technion – Israel Institute of Technology, Haifa, Israel
Mark Gandelman, Schulich Faculty of Chemistry, Technion – Israel Institute of Technology, Haifa, Israel

Metal-free radical halogenation is the most desirable method for C-H activation of unactivated alkanes to produce haloalkanes. However, iodination of hydrocarbons is a highly challenging reaction. The reason for that is the endothermic nature of the reaction between alkanes and iodine. Formation of iodoalkanes from aliphatic hydrocarbons becomes thermochemically favored if oxyl or other strongly electrophilic radicals are used as hydrogen-atom abstractors. Even though, such examples are relatively rare.

Recently a new reagent 1-iodotrimethylhydantoin was developed in our group.  We  report that this compound is an extremely powerful radical iodination agent. Its unique properties enable us to perform direct iodination of saturated hydrocarbons with high yields. Moreover, the reaction could be successfully applied at the benzylic position. To the best of our knowledge, this is the first example of a Wohl-Ziegler iodination reaction.