<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>By using the bifunctional chiral tertiary amino‐thiourea catalyst STC, a series of chiral fluorinated isoxazol‐5(4H)‐ones containing a fluorine‐substituted quarternary stereocenter are obtained in high yields with high enantio‐ and diastereoselectivities.</p> </abstract>