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

Area of Science:

• Organic Chemistry
• Electrochemistry
• Hypervalent Iodine Chemistry

Background:

• Hypervalent iodine compounds are versatile reagents in organic synthesis.
• Controlling the oxidation state and reactivity of hypervalent iodine is crucial for developing new synthetic transformations.

Purpose of the Study:

• To demonstrate sequential disproportionation reactions for selective electron-hole aggregation at hypervalent iodine centers.
• To achieve multielectron oxidation using a one-electron potential through controlled disproportionation.

Main Methods:

• Anodic generation of iodanyl radicals.
• Sequential disproportionation reactions involving iodanyl and iodosylbenzene intermediates.
• Characterization of reaction products, including iodoxybenzene derivatives.

Main Results:

• Selective aggregation of two- or four electron-holes at a hypervalent iodine center was achieved.
• Anodic generation of iodanyl radicals led to iodosylbenzene derivatives.
• Subsequent disproportionation yielded iodoxybenzene, demonstrating controlled oxidation.

Conclusions:

• Sequential disproportionation offers a novel pathway for selective electron-hole aggregation in hypervalent iodine chemistry.
• This methodology enables efficient multielectron oxidation at a low potential, expanding synthetic capabilities.