ent-Eudesmane-Type Sesquiterpenoids from the Chinese Liverwort Chiloscyphus polyanthus var. rivularis ^[*]

Abstract

Seven new ent-eudesmane-type sesquiterpenoids (1–7) and six known analogues (8–13) were isolated from the Chinese liverwort Chiloscyphus polyanthus var. rivularis. Their structures were determined from analysis of MS and NMR spectroscopic data and single-crystal X-ray diffraction. A cytotoxic evaluation showed that compound 1 exhibited weak inhibitory activity against the A549 cancer cell line with an IC₅₀ value of 27.7 µM.

Key words

Chiloscyphus polyanthus var. rivularis - Lophocoleaceae - liverwort - ent-eudesmane - single-crystal X-ray diffraction - cytotoxic activity

^* Dedicated to Professor Dr. Dr. h. c. mult. Kurt Hostettmann recognition of his outstanding contribution to natural product research.

• References

• 1 Asakawa Y. Chemical constituents of Hepaticae. In: Herz W, Grisebach H, Kirby GW, editors Progress in the chemistry of organic natural products, Vol. 42. Vienna: Springer; 1982: 1-285
• 2 Asakawa Y. Chemical constituents of the bryophytes. In: Herz W, Kirby WB, Moore RE, Steglich W, Tamm C, editors Progress in the chemistry of organic natural products, Vol. 65. Vienna: Springer; 1995: 1-618
• 3 Zinsmeister HD, Becker H, Eicher T. Bryophytes, a source of biologically active, naturally occurring material?. Angew Chem Int Ed 1991; 30: 130-147
• 4 Asakawa Y. Chemosystematics of the Hepaticae. Phytochemistry 2004; 65: 623-699
• 5 Asakawa Y, Ludwiczuk A, Nagashima F. Chemical constituents of bryophytes: bio- and chemical diversity, biological activity, and chemosystematics. In: Kinghorn AD, Falk H, Kobayashi J, editors Progress in the chemistry of organic natural products, Vol. 95. Vienna: Springer; 2013: 1-796
• 6 Ma B, Lu ZQ, Guo HF, Lou HX. Rearranged calamenene and eudesmane sesquiterpenoids from two Chinese liverworts. Helv Chim Acta 2007; 90: 52-57
• 7 Toyota M, Saito T, Asakawa Y. The absolute configuration of eudesmane-type sesquiterpenoids found in the Japanese liverwort Chiloscyphus polyanthos . Phytochemistry 1999; 51: 913-920
• 8 Xie CF, Sun B, Guo DX, Qu JB, Lou HX. Terpenoids from the Chinese liverwort Chiloscyphus polyanthus . Helv Chim Acta 2011; 94: 534-538
• 9 Wu C, Gunatilaka AA, Mccabe FL, Johnson RK, Spjut RW, Kingston DG. Bioactive and other sesquiterpenes from Chiloscyphus rivularis . J Nat Prod 1997; 60: 1281-1286
• 10 Cullmann F, Schuld FM, Becker H, Schmidt A. Lignans from the liverworts Lepidoziain curvata, Chiloscyphus polyanthos and Jungermannia exsertifolia ssp. cordifolia . Phytochemistry 1999; 52: 1647-1650
• 11 Toyota M, Nakaishi ERI, Asakawa Y. Eudesmane-type sesquiterpenoids from the liverwort. Phytochemistry 1996; 41: 833-836
• 12 Kutney JP, Singh AK. The chemistry of thujone. V. Thujone as a chiral synthon for the preparation of sesquiterpenes. Synthesis of (+)-carissone. Can J Chem 1982; 60: 1842-1846
• 13 Guo DX, Zhu RX, Wang XN, Wang LN, Wang SQ, Lin ZM, Lou HX. Scaparvin A, a novel caged cis-clerodane with an unprecedented C-6/C-11 bond, and related diterpenoids from the liverwort Scapania parva . Org Lett 2010; 12: 4404-4407
• 14 Wang LN, Zhang JZ, Li X, Wang XN, Xie CF, Zhou JC, Lou HX. Pallambins A and B, unprecedented Hexacyclic 19-nor-secolabdane diterpenoids from the Chinese liverwort Pallavicinia ambigua . Org Lett 2012; 14: 1102-1105
• 15 Zhou JC, Zhang JZ, Cheng AX, Xiong YX, Liu L, Lou HX. Highly rigid labdane-type diterpenoids from a Chinese liverwort and light-driven structure diversification. Org Lett 2015; 17: 3560-3563
• 16 Lin ZM, Guo YX, Gao YH, Wang SQ, Wang XN, Xie ZY, Niu HM, Chang WQ, Liu L, Yuan HQ, Lou HX. ent-Kaurane diterpenoids from Chinese liverworts and their antitumor activities through Michael addition as detected in situ by a fluorescence probe. J Med Chem 2015; 58: 3944-3956
• 17 Raharivelomanana P, Bianchini JP, Faure R, Cambon A, Azzaro M. Two guaiane and eudesmane-type sesquiterpenoids from Neocallitropsis pancheri . Phytochemistry 1996; 41: 243-246
• 18 Fan CQ, Zhan ZJ, Li H, Yue JM. Eudesmane-type sesquiterpene derivatives from Saussurea conica . Helv Chim Acta 2004; 87: 1446-1451
• 19 Alley MC, Scudiero DA, Monks A, Hursey ML, Czerwinski MJ, Fine DL, Abbott BJ, Mayo JG, Shoemaker RH, Boyd MR. Feasibility of drug screening with panels of human tumor cell lines using a microculture tetrazolium assay. Cancer Res 1988; 48: 589-601
• 20 Connolly JD, Harrison LJ, Huneck S, Rycroft DS. (+)-Eudesm-3-ene-6β,7α-diol from the liverwort Lepidozia reptans . Phytochemistry 1986; 25: 1745-1747
• 21 Paul C, König WA, Wu CL. Sesquiterpenoid constituents of the liverworts Lepidozia fauriana and Lepidozia vitrea . Phytochemistry 2001; 58: 789-798
• 22 Shu YF, Wei HC, Wu CL. Sesquiterpenoids from liverworts Lepidozia vitrea and L. Fauriana . Phytochemistry 1994; 58: 789-798
• 23 Shy HS, Wu CL. Eudesmane-type sesquiterpenoids from the liverwort Lepidozia fauriana . J Asian Nat Prod Res 2006; 8: 723-731
• 24 Asakawa Y, Toyota M, Nagashima F, Hashimoto Y, Hassane LE. Sesquiterpene lactones and acetogenin lactones from the Hepaticae and chemosystematics of the liverworts Frullania, Plagiochila and Porella . Heterocycles 2001; 54: 1057-1093
• 25 Toyota M, Asakawa Y. Sesquiterpenoids from the liverwort Bazzania fauriana . Phytochemistry 1988; 27: 2155-2159
• 26 Dolomanov OV, Bourhis LJ, Gildea RJ, Howard JAK, Puschmann H. OLEX2: a complete structure solution, refinement and analysis program. J Appl Cryst 2009; 42: 339-341
• 27 Sheldrick GM. A short history of SHELX. Acta Crystallogr A64. Acta Cryst 2008; 64: 112-122