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

Abstract

Because of its hyper-leaving ability, as well as its strong oxidizing ability, diaryl(triflato)-λ³-iodane transfers one of the aryl groups to iodoarenes simply upon gentle heating (>85 °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-λ³-iodanes.