Multisite Proton-Coupled Electron Transfer Enables Iodanyl Radical Catalysis.

ABSTRACT: The utility of hypervalent iodine reagents is often ascribed to the selective two-electron redox events that interconvert I(I), I(III), and I(V) species during substrate oxidation. We recently reported 1,2-diiodoveratrole (4a) as an efficient catalyst for intramolecular oxidative C-H/N-H coupling and proposed that N-H activation was accomplished by an iodanyl radical (i.e., an I(I)/I(II) catalytic cycle) without accessing the corresponding I(III) derivative. Transient iodanyl radicals have been proposed during reductive activation of I(III) reagents, but the role of I(II) intermediates in substrate activation is underexplored. Here, we report a combined experimental and computational investigation of N-H activation and C-N coupling promoted by iodanyl radicals. The assembled data in

SUBMITTER: Thai P 

PROVIDER: S-EPMC12679642 | biostudies-literature | 2025 Dec

REPOSITORIES: biostudies-literature