Mild preparation of functionalized [2.2]paracyclophanes via the Pummerer rearrangement

2.2]Paracyclophanes, incorporating functional groups in the aliphatic bridges, suitable for elimination to give 2.2]paracyclophanedienes, are synthesized through a novel approach. It relies on a double Pummerer rearrangement on dithiacyclophane precursors, followed by ring contraction through a photochemical sulfur extrusion, and it is compatible with aryl moieties possessing very different electronic properties.