<jats:p>An optimized protocol for the preparation of fluorine‐containing acyclic enones, which are promising building blocks for the preparation of a large variety of fluorinated compounds was developed. These enones easily react with secondary amines to form fluorine‐containing 3‐aminocyclopent‐2‐enones via 4‐amino‐2,3‐dihydrofuran‐2‐ols. The peculiar mechanism involving an intramolecular electrocyclization as a key step is proposed.</jats:p>