Naturally occurring spirostanol saponins bear a chacotriose, α-l-rhamnopyranosyl-(1→ 2)-[α- l-rhamnopyranosyl-(1→ 4)]-β-d-glucopyranose residue as the oligosaccharide moiety which is believed to be important for biological activity. Herein the development of a concise, combinatorial method for the synthesis of two series of glycan variants at the 2′ and/or 4′ positions of chacotriose is described and the structure–activity relationships of the glycone ...