A general and efficient synthesis of trifluoromethyl-substituted 5-alkylidene-1,3-dioxolanes using AgNO 3 and DBU cooperatively catalyzed domino reaction of propargylic alcohols and trifluoromethyl ketones is described. The reaction tolerates a broad range of functional groups, and the desired products are obtained in good to excellent yields (62-99%) with acceptable diastereoselectivities. a Reaction conditions: 1 (0.3 mmol), 2 (0.36 mmol), AgNO 3 (10 mol%), DBU (10 mol%), toluene (1.0 ml), r.t., 24 h. b Isolated yield. c Determined using 19 F NMR.