Two New Highly Oxygenated Spirostanol Saponins from Paris polyphylla var. stenophylla

Natural Products and Bioprospecting, Jun 2016

Ling-Yu Jin, Ting-Xiang Lu, Xu-Jie Qin, Wei Ni, Huan Yan, Yu Chen, Hui Liu, Hong-Ping He, Hai-Yang Liu

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Two New Highly Oxygenated Spirostanol Saponins from Paris polyphylla var. stenophylla

Two New Highly Oxygenated Spirostanol Saponins from Paris polyphylla var. stenophylla Hong-Ping He . Hai-Yang Liu 0 1 2 Ling-Yu Jin . Ting-Xiang Lu . Xu-Jie Qin . 0 1 2 Wei Ni . Huan Yan . Yu Chen . Hui Liu . 0 1 2 0 Y. Chen H. Liu University of Chinese Academy of Sciences , Beijing 100049 , China 1 L.-Y. Jin T.-X. Lu X.-J. Qin W. Ni H. Yan Y. Chen H. Liu H.-Y. Liu (&) State Key Laboratory of Phytochemistry and Plant Resources in West China, Kunming Institute of Botany, Chinese Academy of Sciences , Kunming 650201 , China 2 L.-Y. Jin H.-P. He (&) College of Pharmacy and Chemistry, Dali University , Dali 671000 , China Phytochemical investigation of the rhizomes of Paris polyphylla var. stenophylla led to the isolation of two new highly oxygenated spirostanol saponins, named paristenosides A (1) and B (2), together with seven known compounds. Their structures were established mainly on the base of NMR spectroscopic techniques and mass spectrometry, as well as chemical methods. In addition, the cytotoxicity of the two new saponins was tested. Graphical Abstract Two new highly oxygenated spirostanol saponins, paristenosides A (1) and B (2), were isolated from the rhizomes of Paris polyphylla var. stenophylla. Their structures were established mainly based on NMR spectroscopic techniques and mass spectrometry, as well as chemical methods. Paris polyphylla var; stenophylla 1 Introduction The genus Paris (Liliaceae) comprises about 24 species, which grows as perennial rhizomatous herbs in the Eurasian continent from temperate zone to the tropics [ 1 ]. Rhizoma Paridis (‘Chonglou’ in Chinese), the dried rhizomes of P. polyphylla var. yunnanensis and P. polyphylla var. chinensis, have been recorded in the Pharmacopoeia of the People’s Republic of China as a traditional Chinese medicine for the treatment of traumatic injuries, insect and snake bites, and sore throat [ 2 ]. Plants of the genus Paris are known as a rich source of steroidal saponins, which have attracted great interests for their structural diversity and various bioactivities such as anti-tumor [ 3, 4 ], hemostatic [5], and antifungal [ 6 ] effects. In recent years, our group focuses the research on the chemical constituents, bioactivity, and sustainable utilization of resources of the genus [ 7–11 ]. P. polyphylla var. stenophylla Franch. is one of the variations of P. polyphylla and has been used as a herbal medicine to treat skin furuncle and skin tinea, stop bleeding, and move clean blood and bad blood out by the Yi nationality of Liangshan in Sichuan Province [ 12 ]. Due to having certain resources, its rhizomes have been as the main steam commodities of Rhizoma Paridis. However, there are a few reports about the research of its material basis [ 13 ]. In order to clarify its chemical quality, we performed a phytochemical investigation of the rhizomes of P. polyphylla var. stenophylla. As a result, two new polyhydroxylated steroidal saponis, named paristenosides A (1) and B (2), were isolated from the title species. Meanwhile, seven known compounds were obtained and identified as paris saponin H (3) [ 14 ], Tg (4) [ 15 ], Pb (5) [ 16 ], Th (6) [ 17 ], Methyl-Th (7) [ 18 ], parispseudoside A (8) [ 19 ] and b-ecdysone (9) [ 16 ]. In the current paper, we report the isolation, structural elucidation, and cytotoxicity of the two new compounds (Fig. 1). 2 Results and Discussion Paristenoside A (1) was isolated as a white amorphous powder. Its molecular formula, C50H80O25, was assigned by the positive-ion HR-ESI-MS (m/z 1103.4881 [M ? Na]?, calcd for 1103.4881) and 13C NMR data (Tables 1, 2). The IR spectrum displayed absorption bands ascribable to hydroxy (3426 cm-1) and olefinic bond (1631 cm-1) functionalities. The 13C NMR spectrum showed signals for a ketal carbon at dC 111.5, a trisubstituted olefin carbons at dC 139.4 (s) and 124.6 (d), and three methyls at dC 17.0, 15.0, and 13.1, which were characteristic of a D5,6-spirostanol skeleton as an aglycone [ 7 ]. Its 1H NMR spectrum showed two singlet signals for two tertiary methyls at dH 1.38 and 1.13, one doublet signal for a secondary methyl at dH 1.03 (d, J = 6.8 Hz), an olefinic proton at dH 5.55 (br d, J = 5.5 Hz), as well as four anomeric protons at dH 6.41 (br s), 5.24 (d, J = 7.8 Hz), 4.91 (d, J = 7.6 Hz), and 4.78 (d, J = 7.7 Hz), which suggested the presence of four sugar units. In addition, one methyl at dH 1.71 (d, J = 6.0 Hz) was the methyl of one 6-deoxyhexopyranose residue. Comparison of the 1H and 13C NMR spectra of 1 with those of padelaoside A [ 20 ] revealed that 1 possessed the same polyhydroxylated aglycone [(23S,24S,25S)-spirost-5-ene-1b,3b,21,23,24pentol] as that of padelaoside A, which could be further verified by detailed 2D NMR data analysis (Figs. 2, 3). Furthermore, the result of acid hydrolysis and GC analysis of 1 with its corresponding trimethylsilated L-cysteine adducts afforded D-glucose, D-galactose, D-xylose, and L-rhamnose. T (...truncated)


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Ling-Yu Jin, Ting-Xiang Lu, Xu-Jie Qin, Wei Ni, Huan Yan, Yu Chen, Hui Liu, Hong-Ping He, Hai-Yang Liu. Two New Highly Oxygenated Spirostanol Saponins from Paris polyphylla var. stenophylla, Natural Products and Bioprospecting, 2016, pp. 205-210, Volume 6, Issue 4, DOI: 10.1007/s13659-016-0102-x