Synergistic Iodanyl Radical and Photoredox Dual Catalysis for Direct C–H Bond Functionalization

Iodanyl radical catalysis represents a frontier in hypervalent iodine catalysis, offering unique reactivity distinct from those of traditional I(I)/I(III) and I(III)/I(V) systems. This study presents an innovative photocatalytic strategy for generating and harnessing iodanyl radicals through an efficient I(I)/I(II) catalytic cycle. Using visible-light photocatalysis to convert aryl iodides, we achieve precise control over the formation of iodanyl radical intermediates under redox-neutral conditions. The developed system exhibits versatility, particularly in the activation of alcohols as hydrogen atom transfer catalysts. We show the power of this iodanyl radical catalysis in challenging C–H bond functionalizations, including the activation of light hydrocarbons such as methane, ethane, and propane. Mechanistic investigations reveal the crucial role of iodanyl species in facilitating HAT processes. This work expands the scope of hypervalent iodine chemistry and provides a valuable tool for synthetic organic chemistry, opening avenues for previously challenging transformations.