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 S(N)2 ' 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.