Detrifluoroacetylative in Situ Generated Cyclic Fluorinated Enolates for the Preparation of Compounds Featuring a C–F Stereogenic Center

[Image: see text] Practical methods for the preparation of selectively fluorinated compounds are in extremely high demand in nearly every sector of the pharmaceutical and agrochemical industries. Here we provided an account of the recent methodological breakthrough dealing with detrifluoroacetylative in situ generation of cyclic fluoro-enolates and their application for the preparation of various polyfunctional compounds featuring quaternary C–F stereogenic carbon. The reactions include aldol, Mannich, Michael addition reactions, S(N)2/S(N)2′ alkylations, and the additions to azo compounds. The detrifluoroacetylative protocol for in situ generation of cyclic fluoro-enolates is operationally simple and scalable and proceeds at ambient temperature. Generally, the stereochemical outcome, controlled by the stoichiometric chiral auxiliary of the chiral catalyst, is synthetically useful, allowing preparation of enantiomerically pure compounds of high pharmaceutical potential.