Synthesis of γ-DDB, which is another family member of α-DDB (dimethyl 4, 4′-dimethoxy-5, 6, 5′, 6′-dimethylenedioxybiphenyl-2, 2′-dicarboxylate), is described. The unsymmetric isomer (γ-DDB) was constructed by a linker-directed intramolecular Ullmann coupling reaction, followed by the cleavage of the linker and re-esterification.