<jats:title>Abstract</jats:title><jats:p>Saponins have been extracted from the seed of <jats:italic>Dodonaea attenuata</jats:italic> and converted to prosapogenins by mild acid hydrolysis. Partially acetylated derivatives of the sapogenin, R<jats:sub>1</jats:sub>‐barrigenol, were characterized by extensive two dimensional nuclear magnetic resonance spectroscopy. The complete assignments of <jats:sup>1</jats:sup>H and <jats:sup>13</jats:sup>C resonances and nuclear Overhauser effects of these partly acetylated sapogenins has allowed a straightforward assignment of the structures of the prosapogenins, including the location of the individual ester groups and the presence of artefacts from the acidic hydrolysis conditions.