AbstractAsiaticoside (1), namely, 2α,3β,23-trihydroxy-urs-12-en-28-oic-O-α-l-rhamnopyranosyl-(14)-β-d-glucopyranosyl-(16)-β-d-glucopyranoside, the major active biomarker of the traditional medicinal plant Centella asiatica, has been synthesized for the first time. The strategy features a late-stage gold(I)-catalyzed glycosidic condensation of a triterpenoid acid and a trisaccharide ortho-hexynylbenzoate. The overall preparation required a total 31 steps with the longest linear sequence occurring over 14 steps in a 6 % overall yield and starting from ursolic acid (3β-hydroxy-urs-12-en-28-oic acid).