Highly chemo- and regioselective substrate-directed benzannulation of trisubstituted CF3-alkenes and 2-benzylidenemalononitriles or 2-nitroallylic acetates has been achieved via Michael-initiated [4 + 2] or Rauhut–Currier-initiated [3 + 3] annulation. These protocols enable the rapid assembly of structurally important tri-fluoromethylarene cores featuring five or four contiguous functional groups, affording a broad spectrum of products with diverse substituents in generally high yields. These products could be facilely transformed into structurally diverse molecules of synthetic and medicinal interest.
