Abstract A variety of enamine carboxylic esters and enaminones were converted to the biologically interesting fluorinated 2 H ‐azirines through reactions with PhIF 2 generated in situ by PhIO and Et 3 N ⋅ 3HF in 1,2‐dichroloethane, which features the hypervalent iodine reagents‐mediated introduction of fluorine atom and formation of the 2 H ‐azirine skeleton under metal‐free conditions. The domino reaction is postulated to proceed via a PhIF 2 ‐mediated oxidative fluorination and a subsequent azirination of the fluorinated enamine intermediates. magnified image