Abstract An Ullmann reaction of the chiral bifunctional substrate containing two 1-bromo-2-naphthyl moieties, (S)-2,2′-bis(1-bromo-2-naphthylcarbonyloxy)-1,1′-binaphthyl, gives an intramolecularly coupled 12-membered cyclic diester in a 36% isolated yield. The intramolecular coupling reaction proceeds with virtually complete dia-stereoselectivity to induce S-chirality into the newly formed bond between the two naphthyl units.