Two minor saponins obtained from the methanolic extract of the leaves of Ilex paraguariensis have been characterised by 13C‐NMR, 1H‐NMR, API‐MS and chemical hydrolysis as oleanolic acid‐3‐O‐{β‐D‐glucopyranosyl‐(1 → 3)‐α‐L‐arabinopyranosyl}‐(28 → 1)‐β‐D‐glucopyranosyl ester (guaiacin B) and oleanolic acid‐3‐O‐{β‐D‐glucopyranosyl‐(1 → 3)‐{α‐L‐rhamnopyranosyl‐(1 → 2)}‐α‐L‐arabinopyranosyl}‐(28 → 1)‐β‐D‐glucopyranosyl ester (nudicaucin C). Both are isomeric forms of the known matesaponins 1 (MSP 1) and 2 (MSP 2) and differ only by the nature of the aglycone: they have oleanolic acid instead of ursolic acid, as found in the matesaponins. These minor saponins have not been fully separated from their major isomers MSP 1 and 2 and were characterised by in‐mixture NMR analysis, LC‐MS and LC‐MS
n experiments. Copyright © 2001 John Wiley & Sons, Ltd.