Low-Cost, Safe, and Anion-Flexible Method for the Electrosynthesis of Diaryliodonium Salts

An electrochemical approach toward the synthesis of diaryliodonium salts based on anodic C-I coupling between aryl iodides and arenes is presented. In contrast to previous protocols, our method requires no chemical oxidants, strong acids, or fluorinated solvents. A further advantage is that by use of the appropriate supporting electrolyte, the counterion of choice can be introduced, which is time- and cost-saving as compared to postsynthesis ion exchange. This "anion-flexibility" is particularly interesting when considering the pronounced effect of the counterion on the reactivity of diaryliodonium species in aryl transfer reactions. The scope of our method comprises 24 examples with isolated yields of up to 99%. Scalability was demonstrated by the synthesis on a gram scale. Furthermore, it was shown that the diaryliodonium-containing post-electrolysis solution can be used without further workup as a reactive medium for O-arylation reactions. Finally, a series of para-substituted diaryliodonium compounds was studied using linear sweep voltammetry on a microelectrode and analyzed with respect to the influence of the electronic structure on the redox behavior.