Binaphthyl-based chiral macrocyclophanes with variously sized cavities: D n -symmetrical structure constructed from unidirectionally-inclined rod segments.

Abstract: As new and chiral macrocyclophanes with unique structures, variously sized Pn and Mn (n=2–7=number of ‘rod’ segments) with D 2–D 7 symmetry were constructed by alternating connection of axially chiral binaphthyls and linear biphenyls via –CH2O– moieties, so that the macrocycle consists of multiple rod-like naphthalene–biphenyl–naphthalene units linked together at the binaphthyl bonds. The dihedral angle of the two naphthalene rings of binaphthyl is restricted to around 90°, and the calculated values of strain energy difference per naphthalene–biphenyl unit in P2–P7 are almost independent of the macrocycle size, presumably owing to the flexibility of the –CH2O– connectors. [Copyright &y& Elsevier]