Mechanistic Study on Aryl-Exchange Reaction of Diaryl-λ3-iodane with Aryl Iodide

Because of its hyper-leaving ability, as well as its strong oxidizing ability, diaryl(triflato)-lambda(3)-iodane transfers one of the aryl groups to iodoarenes simply upon gentle heating (>85 degrees C) in nonpolar solvents. We have performed an in-depth mechanistic study of this unusual aryl transfer reaction. A combination of experimental (product analysis, kinetic study, and substituent effects) and density functional theoretical approaches revealed that the reaction proceeds through a concerted bimolecular transition state, in which ipso-carbon binds loosely to both iodine centers. We also evaluated electronic effects on the thermodynamic stability of diaryl-lambda(3)-iodanes.