Abstract
Three new polyoxypregnane glycosides, marsdenosides I–K (1–3), were isolated from the stem of Marsdenia tenacissima. The structures were elucidated on the basis of in‐depth spectroscopic analyses, and by means of chemical evidence. Marsdenoside I (= (3β,5α,11α,12β,14β,17α,20R)‐3‐[(2,6‐dideoxy‐4‐O‐(6‐deoxy‐3‐O‐methyl‐β‐D‐allopyranosyl)‐3‐O‐methyl‐β‐D‐arabino‐hexopyranosyl)oxy]‐8,20 : 11,20‐diepoxypregnane‐12,14‐diol; 1) is the first C21 steroidal glycoside with a rigid cage. Also, the isolation of 1 demonstrated that tenacigenin A (1a) is a true natural product as well, rather than an artifact.

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