Elsevier

Phytochemistry

Volume 69, Issue 10, July 2008, Pages 2070-2080
Phytochemistry

Phenolic compounds and rare polyhydroxylated triterpenoid saponins from Eryngium yuccifolium

https://doi.org/10.1016/j.phytochem.2008.03.020Get rights and content

Abstract

Phytochemical investigation on the whole plant of Eryngium yuccifolium resulted in the isolation and identification of three phenolic compounds (13) and 12 polyhydroxylated triterpenoid saponins, named eryngiosides A–L (415), together with four known compounds kaempferol-3-O-(2,6-di-O-trans-p-coumaroyl)-β-d-glucopyranoside (16), caffeic acid (17), 21β-angeloyloxy-3β-[β-d-glucopyranosyl-(1→2)]-[β-d-xylopyranosyl-(1→3)]-β-d-glucuronopyranosyloxyolean-12-ene-15α,16α,22α,28-tetrol (18), and saniculasaponin III (19). This study reports the isolation of these compounds and their structural elucidation by extensive spectroscopic analyses and chemical degradation.

Graphical abstract

The isolation and structural elucidation of three phenolic compounds (13) and 12 saponins eryngiosides A–L (415) from Eryngium yuccifolium Michx. are reported.

  1. Download : Download full-size image

Introduction

Eryngium L. is a cosmopolitan genus (Apiaceae) of about 317 taxa (Wörz, 1999). Some species, such as E. maritimun L. (Lisciani et al., 1984), E. campestre L. (Baytop, 1999), and E. foetidum L. (Editorial Committee of Zhonghua Bencao, 1999), have been used in folk medicine. Eryngium yuccifolium Michx., known as “rattlesnake master”, “button eryngo”, or “button snakeroot”, is a perennial species naturally distributed in eastern North America. Traditionally, the poultice, infusion or tincture made from the roots of this species was used for snakebites, fevers, or female reproductive disorders (Weiner, 1980, Foster and Duke, 1990, Moerman, 1998). However, there is no report available on the chemical and bioactive investigation on this species.

Previous phytochemical investigations on the Eryngium genus indicated the presence of flavonoids (Ikramov et al., 1973, Zarnack et al., 1979, Hiller et al., 1981, Kartnig and Wolf, 1993, Hohmann et al., 1997), essential oil (Brophy et al., 2003, Ayoub et al., 2003, Ayoub et al., 2006, Pala-Paul et al., 2005a, Pala-Paul et al., 2005b, Pala-Paul et al., 2006), coumarins (Erdelmerier and Sticher, 1985), a rosmarinic acid derivative (Le Claire et al., 2005), and saponins (Hiller et al., 1972, Hiller et al., 1974a, Hiller et al., 1974b, Hiller et al., 1975, Hiller et al., 1976a, Hiller et al., 1976b, Hiller et al., 1977, Hiller et al., 1978, Ikramov et al., 1974, Anam, 2002, Kartal et al., 2005, Kartal et al., 2006). The main saponins from this genus belong to polyhydroxylated triterpenoid glycosides with ester functions. This class of saponins has been found in various groups of plants such as Aesculus chinensis L. (Hippocastanaceae) (Yang et al., 1999, Zhang et al., 1999a, Zhao et al., 2001, Zhao and Yang, 2003, Wei et al., 2004), Pittosporum tobira (Thunb.) Ait. (Pittosporaceae) (D’Acquarica et al., 2002), Sanicula elata var. chinensis Makino (Apiaceae) (Matsushita et al., 2004), and Harpullia austro-caledonica Baill. (Sapindaceae) (Voutquenne et al., 2005). Some saponins have been shown to possess anti-inflammatory properties (Matsuda et al., 1997, Sirtori, 2001, Wei et al., 2004), anti-HIV-1 protease activity (Yang et al., 1999), and cytotoxicity for tumor cells (D’Acquarica et al., 2002, Fu et al., 2006, Chan, 2007, Zhang and Li, 2007). Recently, we isolated and identified 25 new polyhydroxylated triterpenoid saponins from North American Aesculus pavia L. (Zhang et al., 2006, Zhang and Li, 2007). The saponins with two acyl groups at C-21 and C-22 had cytotoxic activity against 60 cell lines from nine different human cancers (Zhang and Li, 2007). Our interests in identification of novel bioactive agents from native plants in Texas prompted us to conduct a chemical investigation on E. yuccifolium. In this paper, we report the isolation and structural elucidation of 15 new compounds (115).

Section snippets

Results and discussion

The n-butanol-soluble part partitioned from the ethanol extract of E. yuccifolium was fractionated by a silica gel column to give three fractions A, B and C. Fraction C was subfractionated by an octadecyl-functionalized silica gel (ODS) column to afford fractions C1, C2 and C3. Further separation of these fractions was achieved by preparative HPLC to furnish compounds 119 (see Section 4 for details).

Compounds 1619 are known compounds and were identified by their spectroscopic data as

Conclusions

Recent studies (Kartal et al., 2005, Kartal et al., 2006) indicated that E. campestre contained R1- and A1-barrigenol-based polyhydroxylated triterpenoid glycosides (saponins) with two or three sugar units. This study shows that the saponins in E. yuccifolium are more variable both in their aglycone and oligosaccharidic chain moieties with different components and sequences. The type of polyhydroxylated triterpenoid glycosides usually possessed acyl functions at C-21, C-22, and C-28 positions,

General experimental procedures

NMR experiments were performed on a Bruker 600 MHz NMR instrument, with NMR spectroscopic data reported as δ (ppm) values and referenced to the solvent used. HRMALDIMS were acquired on a MALDI TOF instrument (Applied Biosystems Voyager STR), where HRESIMS were obtained using an Electrospray instrument (MDS Sciex Pulsar Qstar). UV spectra were recorded in MeOH with a μ Quant spectrophotometer (Bio-Tek Instruments Inc.). Optical rotation values were measured on a JASCO P-1010 polarimeter.

Acknowledgements

This study is funded by the U.S. CDC Grant (R01 CI000315-01). The authors would like to thank the Keck/IMD NMR Center, which is funded by the W.M. Keck Foundation and the University of Houston; Dr. Youlin Xia for NMR analysis assistance; and Dr. Shane Tichy of Texas A&M University for HRESI-MS analysis.

References (55)

  • Z.Z. Zhang et al.

    Triterpenoid saponins from the fruits of Aesculus pavia

    Phytochemistry

    (2006)
  • Z.Z. Zhang et al.

    Cytotoxic triterpenoid saponins from the fruits of Aesculus pavia L

    Phytochemistry

    (2007)
  • E.M. Anam

    A novel triterpenoid saponin from Eryngium foetidum

    Indian J. Chem., Sect. B: Org. Chem. Incl. Med. Chem.

    (2002)
  • N.A. Ayoub et al.

    An unique N-propyl sesquiterpene from Eryngium creticum L. (Apiaceae)

    Pharmazie

    (2003)
  • N. Ayoub et al.

    Essential oils and a novel polyacetylene from Eryngium yuccifolium Michaux. (Apiaceae)

    Flav. Fragr. J.

    (2006)
  • T. Baytop

    Turkiye de Bitkilerle Tedavi-Gecmisten Bugune (Therapy with Medicinal Plants in Turkey-Past and Present)

    (1999)
  • J.J. Brophy et al.

    Essential oil of Eryngium L. species

    J. Essent. Oil Res.

    (2003)
  • J. Budzianowski et al.

    Phenylpropanoid esters from Lamium album flowers

    Phytochemistry

    (1995)
  • Editorial Committee of Zhonghua Bencao, 1999. Zhonghua Bencao, vol. 5, Shanghai Science and Technology Press, Shanghai,...
  • C.A. Erdelmerier et al.

    Coumarin derivatives from Eryngium campestre L

    Planta Med.

    (1985)
  • S. Foster et al.

    A Field Guide to Medicinal Plants. Eastern and Central N. America

    (1990)
  • G. Fu et al.

    Cytotoxic oxygenated triterpenoid saponins from Symplocos chinensis

    J. Nat. Prod.

    (2006)
  • K. Hiller et al.

    Isolation of barringtogenol C-esters from Eryngium planum L

    Pharmazie

    (1972)
  • K. Hiller et al.

    The leaf sapogenin spectrum in Eryngium planum L. 20. Contribution on the content of several Saniculoideae

    Pharmazie

    (1974)
  • K. Hiller et al.

    Betulinic acid-a sapogenin in Eryngium bromeliifolium Delar. 21. The contents of a saniculoidea

    Pharmazie

    (1974)
  • K. Hiller et al.

    Isolation of new ester sapogenins from Eryngium giganteum M.B 22. Knowledge of various Saniculoideae components

    Pharmazie

    (1975)
  • K. Hiller et al.

    Saponins of Eryngium maritimum L. 25. Contents of various Saniculoideae

    Pharmazie

    (1976)
  • Cited by (0)

    View full text