The utility of intramolecular glycosylation for the synthesis of the 27-membered macrocyclic ring is highlighted in this first total synthesis of the most complex resin glycoside isolated to date -Calysolin IX. Oligosaccharide-containing macrolides core was effectively constructed by TfOH/NIS-promoted intramolecular glycosylation of thioglycosyl donor. As the glycosidic bond must be created en route to target structure, we [a] Mirosław Nawój,
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