The cycloaddition of two moles of benzyne with any two non diametrically opposite furan units of 1 in ananti geometry yields a chiral macrocycle. The chiral anti-1,3-bis-adduct 2 has been isolated, characterised by X-ray crystallography, and converted into the corresponding dinaphthafurophane 4. The X-ray analysis of 4 shows the crystals to contain only a single enantiomer i.e. 4 undergoes spontaneous resolution on crystallisation.