Synthesis of oligomeric 4-(glycosyloxy)benzoate macrocyclic glycosides

Clemoarmanoside A and Clemahexapetoside A, two novel cyclic dimers of 4-(glycosyloxy)benzoates containing the unusual d-allopyranose as one of the sugar units, were synthesized for the first time. The convenient synthetic approach was adapted to the assembly of the symmetrical trimeric, tetrameric, and pentameric congeners. The synthesis clarified the discrepancy in the NMR data reported for the natural products. X-ray diffraction analysis of Clemahexapetoside A revealed that it adopted an armchair conformation with two carbohydrate rings as the arms and two aromatic rings as the back and seat, respectively.