As a rule, reactive free radicals used in organic synthesis are too labile to be isolated, whereas persistent radicals are inert and find limited synthetic application. In the present study, the unusually stable diacetyliminoxyl radical was presented as a "golden mean" between transient and stable unreactive radicals. It was successfully employed as a reagent for oxidative C-O coupling with β-dicarbonyl compounds. Using this model radical the catalytic activity of acids, bases and transition metal ions in free-radical coupling was revealed.