Mechanistic Study on Aryl-Exchange Reaction of Diaryl-λ3-iodane with Aryl Iodide
Yui Masumoto1,2, Kazunori Miyamoto1, Takuto Iuchi3
1Graduate School of Pharmaceutical Sciences, The University of Tokyo , 7-3-1 Hongo Bunkyo-ku, Tokyo 113-0033, Japan.
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.
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