Sulfonamide-Directed Chemo- and Site-Selective Oxidative Halogenation/Amination Using Halogenating Reagents Generated in Situ from Cyclic Diacyl Peroxides.

The combination of cyclic diacyl peroxides with commercially available halide salts as a unique halogenating system is utilized in Hofmann-Löffler-Freytag-type reaction. This strategy allows for the formation of N-chloroamides, δ-brominated products, and even biologically relevant pyrrolidines under mild conditions in moderate to excellent yields. Meanwhile, the preliminary structure of the in situ formed brominating reagent is investigated by NMR and UV/vis analysis.