MnBr 2 ‐Catalyzed Aerobic Oxyazidation of Fluoroolefins: Access to Fluoroalkylated β‐Hydroxy Aliphatic Azides

MnBr 2 ‐catalyzed oxyazidation of fluoroolefins with molecular oxygen and TMSN 3 is reported. This method gives rise to various useful fluoroalkylated β‐hydroxy aliphatic azides in 36%–97% yields. Importantly, this protocol features mild conditions, operationally simple, and gram‐scalable, it tolerates various functional groups and has been applied in the synthesis of diverse attractive bioactive compounds and analogous. Mechanism studies enable the detection of the intermediate and indicate that a radical reaction process is involved. The β‐fluoride elimination of α‐fluoroalkylated radicals via radical‐polar crossover pathway was completely inhibited in this reaction. magnified image