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Five new resin glycosides, calyhedins XI–XV, from Calystegia hederacea

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Abstract

Calystegia hederacea Wall. (Convolvulaceae) is a perennial herbaceous vine that grows widely in India and East Asia. All parts of this plant are used to treat various disorders such as menoxenia and gonorrhea. Four new resin glycosides, calyhedins XI (1)–XIV (4), were isolated from the rhizomes of C. hederacea. A new glycoside, calyhedin XV (5), was isolated from its leaves and stems. Alkaline hydrolysis of 1 and 2 furnished a new glycosidic acid, calyhedic acid G (1a), from 1 and a new acid, calyhedic acid H (2a), from 2 along with 2S-methylbutyric acid and 2R-methyl-3R-hydroxybutyric (2R,3R-nilic) acid. The structures of 1–5, 1a, and 2a were determined using MS and NMR spectral analyses. Compounds 1a and 2a had the same sugar moiety, β-d-glucopyranosyl-(1 → 6)-O-β-d-glucopyranosyl-(1 → 6)-O-β-d-glucopyranosyl-(1 → 3)-[O-β-d-glucopyranosyl-(1 → 3)-O-α-l-rhamnopyranosyl-(1 → 2)]-O-β-d-glucopyranosyl-(1 → 2)-β-d-fucopyranose, while their aglycones were 11S-dihydroxyhexadecanoic acid and 12S-dihydroxyhexadecanoic acid, respectively. These compounds are the first glycosidic acids, with fucose as the monosaccharide component obtained from the resin glycosides of C. hederacea. Compounds 1–5, comprising either 1a or 2a, were heptaglycosides with macrolactone structures, and their sugar moieties were partially acylated with 5 mol of organic acids comprising 2S-methylbutyric, (E)-2-methylbut-2-enoic, and 2R,3R-nilic acids. Compounds 1 and 5 had 22-membered rings, while 2–4 had 28-membered rings. In addition, 1 and 5 exhibited cytotoxic activity against HL-60 human promyelocytic leukemia cells, comparable to that of the positive control cisplatin.

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Acknowledgements

We express our appreciation to Mr. H. Harazono of Fukuoka University for the measurement of the FAB-MS and ESI-TOF-MS. This research was partially supported by a Grant-in-Aid for Scientific Research (C) (JSPS KAKENHI Grant Numbers JP16K08306 and JP20K07117) and by the Research and Study Project of Tokai University General Research Organization (Kanagawa, Japan).

Funding

This research was partially supported by a Grant-in-Aid for Scientific Research (C) (JSPS KAKENHI Grant Numbers JP16K08306 and JP20K07117).

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Authors and Affiliations

  1. School of Agriculture, Tokai University, 871-12 Sugido, Mashiki-Cho, Kamimashiki-Gun, Kumamoto, 861-2205, Japan

    Masateru Ono, Yuki Yamano, Takaaki Shimohara, Nobuyoshi Yuhara, Nodoka Misuda, Hirotaka Nishikawa & Shin Yasuda

  2. Faculty of Pharmaceutical Sciences, Sojo University, 4-22-2 Ikeda, Nishi-Ku, Kumamoto, 860-0082, Japan

    Hiroyuki Miyashita & Hitoshi Yoshimitsu

  3. Faculty of Pharmaceutical Sciences, Fukuoka University, 8-19-1 Nanakuma, Jonan-Ku, Fukuoka, 814-0180, Japan

    Ryota Tsuchihasi, Masafumi Okawa & Junei Kinjo

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  1. Masateru Ono
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  2. Yuki Yamano
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  3. Takaaki Shimohara
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  4. Nobuyoshi Yuhara
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  7. Shin Yasuda
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  8. Hiroyuki Miyashita
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  11. Masafumi Okawa
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  12. Junei Kinjo
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Contributions

Dr. Ono supervised the research, wrote the manuscript, and analyzed the data. Mr. Yamano, Mr. Shimohara, and Mr. Yuhara purified the compounds. Ms. Misuda, Mr. Nishikawa, and Dr. Yasuda were responsible for the antitumor activity. Drs. Miyashita, Yoshimitsu, Tsuchihasi, Okawa, and Kinjo performed instrumental analysis and data analysis.

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Correspondence to Masateru Ono.

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Ono, M., Yamano, Y., Shimohara, T. et al. Five new resin glycosides, calyhedins XI–XV, from Calystegia hederacea. J Nat Med 77, 774–791 (2023). https://doi.org/10.1007/s11418-023-01720-y

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  • DOI: https://doi.org/10.1007/s11418-023-01720-y

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