Abstract The TiCl 4/Zn-mediated intermolecular pinacol coupling of the planar chiral carbonyl compounds [2.2] paracyclophane-4-carbaldehyde, 4-acetyl [2.2] paracyclophane (ketone) and the four regioisomeric 5-, 7-, 12-and 13-methoxy [2.2] paracyclophane-4- carbaldehydes as well as the pTosOH–Zn/Cu-promoted coupling of their N-substituted imines is described. Coupling of the enantiomerically pure substrates (most of carbonyl ...