I(I)/I(II) iodanyl radical catalysis offers distinct reactivity but remains underexplored due to open-shell instability. Here we report a redox-neutral, metal-free dual catalytic platform that merges iodanyl radical catalysis with photoredox catalysis to enable efficient decarboxylative alkylation of carboxylic acids. Diverse primary, secondary, tertiary, and heteroatom-containing substrates are converted to alkyl radicals with broad compatibility. Notably, challenging methylation and difluoromethylation reactions are achieved using readily available acetic acid and difluoroacetic acid as radical precursors. This work expands the synthetic utility of odd-electron hypervalent iodine chemistry as a versatile complement to conventional two-electron paradigms.
Liu et al. (Sun,) studied this question.