A highly enantioselective intramolecular NHC-catalyzed approach for the synthesis of fluoroalkylated benzopyranones and 3-coumaranones with all-carbon quaternary stereocenters is presented. This reaction is catalyzed by N-heterocyclic carbenes (NHCs) and involves annulation reactions between in situ generated acyl anion intermediates and highly substituted trifluoromethyl-β,β-disubstituted Michael acceptors. The method can also be extended to perfluoroalkyl homologues.