Selective Azidooxygenation of Alkenes Enabled by Photo-induced Radical Transfer Using Aryl-λ(3)-azidoiodane Species

[Image: see text] The photolytic radical-induced vicinal azidooxygenation of synthetically important and diverse functionalized substrates including unactivated alkenes is reported. The photoredox-catalyst/additive-free protocol enables intermolecular oxyazidation by simultaneously incorporating two new functionalities; C–O and C–N across the C=C double bond in a selective manner. Mechanistic investigations reveal the intermediacy of the azidyl radical facilitated via the photolysis of λ(3)-azidoiodane species and cascade proceeding to generate an active carbon-centered radical. The late-stage transformations of azido- and oxy-moieties were amply highlighted by assembling high-value drug analogs and bioactive skeletons.