Fluorocyclization of Vinyl Azides for the Formation of 3‐Azido Heterocycles

3‐Azido saturated heterocycles are important for therapeutic‐development but challenging to prepare. Disclosed herein is a novel synthetic strategy for 3‐azido heterocycles via fluorocyclization of the easily available vinyl azides. This transfor‐mation proceeded under mild conditions and provided a wide range of 3‐azido heterocycles in good to excellent yields. Notably, the azido group plays an indispensable role to promote rapid and regioselective fluorocyclization. Moreover, the protocol was highlighted by gram‐scale synthesis and further synthetic transformations. Synthetic Methods. A novel strategy for the synthesis of 3‐azido saturated heterocycles via the fluorocyclization of vinyl azides has been developed. This method furnishes a broad range of 3‐azido oxa/azaheterocycles that are typically difficult to attain with post functionalization.