Selective multi-electron aggregation at a hypervalent iodine center by sequential disproportionation

We demonstrate that sequential disproportionation reactions can enable selective aggregation of two- or four electron-holes at a hypervalent iodine center. Disproportionation of an anodically generated iodanyl radical affords an iodosylbenzene derivative. Subsequent iodosylbenzene disproportionation can be triggered to provide access to an iodoxybenzene. These results demonstrate multielectron oxidation at the one-electron potential by selective and sequential disproportionation chemistry. We report a strategy to aggregate two- or four interfacial electron transfers at an iodine center as an approach to multi-electron electrosynthesis. The intermediates are characterized via UV-vis spectroscopy and single crystal X-ray crystallography.