Elsevier

Phytochemistry

Volume 52, Issue 4, October 1999, Pages 715-722
Phytochemistry

Triterpenoidal saponins from Gleditsia sinensis

https://doi.org/10.1016/S0031-9422(99)00238-1Get rights and content

Abstract

Six bisdesmosidic triterpenoidal saponins, gleditsiosides H-K and gleditsia saponins C′ and E′, were isolated from the anomalous fruits of Gleditsia sinensis. Their structures were established by a combination of extensive NMR (DEPT, DQF-COSY, HETCOR, HOHAHA, HMBC and ROESY) studies and chemical degradation.

Introduction

The medicinal plant Gleditsia sinensis Lam. (Leguminosae) is a perennial arbor widely distributed throughout China. Its anomalous fruits called ‘Zhu Yao Zao’, produced by old or injured plants, have long been known in traditional Chinese medicine as a saponin-rich herbal medicine used for the treatment of apoplexy and as an expectorant and pesticide (Jiangsu New Medical College, 1977). Previous phytochemical studies led to seven new triterpenoidal saponins, named gleditsiosides A–G, together with two known ones (Zhang et al., 1999, Zhang et al., 1999). All nine bisdesmosidic triterpenoidal glycosides were acylated with one or two monoterpenic acids to the sugar moieties. Further examination of the more polar saponin fractions furnished four new saponins, designated as gleditsiosides H, I, J and K (1, 46), and two new natural ones (2, 3), called gleditsia saponins C′ and E′, which were obtained previously from the alkaline hydrolysate of gleditsia saponins C and E isolated from the fruits of Gleditsia japonica. In this contribution, we describe their isolation and structural elucidation by various NMR spectroscopic techniques (including DEPT, DQF-COSY, HOHAHA, HETCOR, HMBC and ROESY experiments) and some chemical degradation.

Section snippets

Results and discussion

Gleditsioside H (1), a white amorphous solid, had a molecular formula of C74H120O37, as determined by 13C NMR spectroscopic data and the [M+Na]+ ion at m/z 1623 and [M+K]+ ion at m/z 1639 in the MALDI-TOF MS (positive ion mode). The seven tertiary methyl carbon signals at δ 15.8, 17.1, 17.5, 23.8, 26.0, 28.3, 33.2 and the two olefinic carbon signals at δ 122.8, 144.1, coupled with the 1H information (seven methyl proton singlets at δ 0.86, 0.89, 0.98, 0.99, 1.10, 1.33, 1.37 and a broad triplet

General procedures

Melting points were measured with a Yanaco microscope apparatus and were uncorrected. Optical rotations were measured with a JASCO DIP-370 digital polarimeter. IR spectra were carried out at a JASCO 300E FTIR spectrometer. MALDI-TOF MS were conducted using a Perseptive Biosystems Voyager DE-STR mass spectrometer. The 1H and 13C NMR spectra were recorded on a JEOL α-500 FT-NMR spectrometer in pyridine-d5 solution and chemical shifts were expressed in δ (ppm) referring to TMS. Diaion HP-20

References (7)

  • S.K. Nigam et al.

    Phytochemistry

    (1997)
  • Z. Jia et al.

    J. Nat. Prod.

    (1998)
  • T. Konoshima et al.

    Chem. Pharm. Bull.

    (1980)
There are more references available in the full text version of this article.

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