Isolation, Structural Elucidation, and Liquid Chromatography–Mass Spectrometry Analysis of Steroidal Glycosides from Polygonatum odoratum

The rhizomes of Polygonatum odoratum represent a traditional Chinese medicine and functional food. A phytochemical investigation resulted in the isolation of eight steroidal glycosides (<b>1</b>–<b>8</b>), including two new compounds, polygonatumosides F (<b>1</b>) and G (<b>2</b>). The structures were elucidated by spectroscopic data and chemical reactions. Compound <b>7</b> showed antiproliferation activity against human hepatocellular carcinoma cell line HepG2 (IC₅₀ of 3.2 μM). The chemical profile and contents of steroidal glycosides of P. odoratum rhizomes collected at different dates and geographical locations were also investigated, indicating that the rational harvest of P. odoratum in spring and autumn is preferable to obtain higher levels of steroidal glycosides. Compounds <b>1</b> and <b>7</b> showed the highest contents in all P. odoratum samples and have potential to serve as chemotaxonomic and chemical markers for quality control of this important plant material. 14-Hydroxylation may be a key step for the biosynthesis of compounds <b>1</b>–<b>7</b>