Base-Mediated Regioselective [3 + 3] Annulation of Alkylidene Malononitriles with Trifluoromethyl Alkenes via Dual C–F Bond Cleavage

A base-mediated regioselective [3 + 3] annulation of alkylidene malononitriles with trifluoromethyl alkenes was described. The reaction proceeds through sequential intermolecular SN2′ and intramolecular SNV-type cyclization by cleaving dual C–F bonds in a trifluoromethyl group, which discriminate multiple carbon-nucleophilic sites using a single base. Various bicycles bearing a monofluorocyclohexene motif were assembled from readily available starting materials under mild conditions via a one-pot cascade approach.