One-Pot Radical Azidooxygenation of Alkenes Enabled by Dibenzothiophenium Salts

Herein, we develop a one-pot and catalyst-free strategy to generate azide and <i>N</i>-oxyl radicals engaging dibenzothiophenium salts and two nonprefunctionalized partners, accessing a variety of azidooxygenated compounds from readily available alkenes. The practicability of this protocol is demonstrated by the broad substrate scope, excellent functional group tolerance, the scale-up reaction, and versatile synthetic elaborations of the resulting products. Mechanistic studies reveal that a radical process is involved in the transformation.