Nitrogen-Centered Organic Persistent Radicals Catalyze Redox-Neutral C─C Bond Forming Reactions.

We report that nitrogen-centered persistent radicals, Kuhn verdazyls, are effective, tunable ground-state redox organocatalysts for single electron transfer (SET)-initiated radical transformations. Verdazyls uniquely emulate catalytic single-electron shuttling, a hallmark of redox catalysis, without light or external stimuli. They enable redox-neutral C─C bond-forming reactions, such as C─H arylation and C─H trifluoromethylation, typically driven by transition metals, photoredox catalysts, or mechanoredox mediators, while avoiding the self-inhibition that limits organic super electron donors and nitroxides in such applications.