A Cu (I)-catalyzed migratory oxidative coupling between nitrones and heterocycles or a methylamine is described. Selective C–C bond-formation proceeds through cleavage of two C (sp3)–H bonds concomitant with C N double bond-migration. The reaction provides an alternating nitrone moiety, allowing for further synthetically useful transformations. Radical clock studies suggest that the nucleophilic addition of nitrones to an oxidatively generated ...