C<sub>14</sub>-polyacetylenol glycosides from the roots of <i>Codonopsis pilosula</i>

<div><p></p><p>Eight new C<sub>14</sub>-polyacetylenol glycosides, containing ene-diyne and ene-yn-ene chromophores named codonopilodiynosides H-M (<b>1</b>–<b>6</b>) and codonopiloenynenosides A and B (<b>7</b> and <b>8</b>), respectively, together with three known analogs lobetyolinin, pratialin B, and lobetyolin (<b>9</b>–<b>11</b>), were isolated from an aqueous extract of the roots of <i>Codonopsis pilosula</i>. Their structures were determined by spectroscopic and chemical methods including 2D NMR data analysis and enzymatic hydrolysis. The absolute configurations of aglycones in <b>1</b>–<b>10</b> were assigned by application of the methoxyphenylacetic acid (MPA) determination rule of Δ<i>δ</i><sup><i>RS</i></sup> values and/or the empirical rule of Mo<sub>2</sub>(OAc)<sub>4</sub>-induced circular dichroism for the vicinal diols, or by comparison of specific rotation values with those of reported compounds. Compounds <b>4</b>–<b>6</b> are the first polyacetylenol glycosides possessing a <i>cis</i>-ene-diyne chromophore from the genus <i>Codonopsis</i>, while <b>8</b> has a rear <i>trans</i>-ene-yn-<i>cis</i>-ene chromophore and a (6<i>S</i>,7<i>S</i>)-6,7-diol unit against a (6<i>R</i>,7<i>R</i>)-6,7-diol unit in the others. The absolute configurations of lobetyolinin (<b>9</b>) and pratialin B (<b>10</b>) were determined for the first time.</p></div>