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

Jin LY, Lu TX, Qin XJ, Ni W, Yan H, Chen Y, Liu H, He HP, Liu HY - Nat Prod Bioprospect (2016)

Bottom Line: 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.In addition, the cytotoxicity of the two new saponins was tested.Two new highly oxygenated spirostanol saponins, paristenosides A (1) and B (2), were isolated from the rhizomes of Paris polyphylla var. stenophylla.

View Article: PubMed Central - PubMed

Affiliation: College of Pharmacy and Chemistry, Dali University, Dali, 671000, China.

ABSTRACT
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. 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.

No MeSH data available.


Key ROESY correlations for the aglycone moiety of paristenoside A (1)
© Copyright Policy - OpenAccess
Related In: Results  -  Collection

License
getmorefigures.php?uid=PMC4940253&req=5

Fig3: Key ROESY correlations for the aglycone moiety of paristenoside A (1)

Mentions: 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 δC 111.5, a trisubstituted olefin carbons at δC 139.4 (s) and 124.6 (d), and three methyls at δC 17.0, 15.0, and 13.1, which were characteristic of a ∆5,6-spirostanol skeleton as an aglycone [7]. Its 1H NMR spectrum showed two singlet signals for two tertiary methyls at δH 1.38 and 1.13, one doublet signal for a secondary methyl at δH 1.03 (d, J = 6.8 Hz), an olefinic proton at δH 5.55 (br d, J = 5.5 Hz), as well as four anomeric protons at δH 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 δH 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-1β,3β,21,23,24-pentol] 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. The large coupling constants (3J1,2 > 7 Hz) were consistent with β-configuration for the glucose, galactose, and xylose, while the α-configuration for the rhamnose was deduced by comparing its 13C NMR spectroscopic data for C-3″ (δC 72.4) and C-5″ (δC 69.5) with those reported in the literature [21]. The sequence and binding sites of the sugar units were determined by following HMBC correlations: δH 6.41 (H-1″ of Rha) with δC 76.3 (C-2′ of Glc), δH 4.91 (H-1″′ of Xyl) with δC 88.3 (C-3′ of Glc), δH 4.78 (H-1′ of Glc) with δC 83.9 (C-1 of the aglycone), and δH 5.24 (H-1″″ of Gal) with δC 81.8 (C-24 of the aglycone). Assignment of all proton and carbon resonances was achieved by interpretation of 1H-1H COSY, HSQC, and HMBC spectra. Based on the above information, the structure of paristenoside A (1) was elucidated as 24-O-β-d-galactopyranosyl-(23S,24S,25S)-spirost-5-ene-1β,3β,21,23,24-pentol-1-O-α-l-rhamnopyranosyl-(1 → 2)-[β-d-xylopyranosyl-(1 → 3)]-β-d-glucopyranoside.Table 1


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

Jin LY, Lu TX, Qin XJ, Ni W, Yan H, Chen Y, Liu H, He HP, Liu HY - Nat Prod Bioprospect (2016)

Key ROESY correlations for the aglycone moiety of paristenoside A (1)
© Copyright Policy - OpenAccess
Related In: Results  -  Collection

License
Show All Figures
getmorefigures.php?uid=PMC4940253&req=5

Fig3: Key ROESY correlations for the aglycone moiety of paristenoside A (1)
Mentions: 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 δC 111.5, a trisubstituted olefin carbons at δC 139.4 (s) and 124.6 (d), and three methyls at δC 17.0, 15.0, and 13.1, which were characteristic of a ∆5,6-spirostanol skeleton as an aglycone [7]. Its 1H NMR spectrum showed two singlet signals for two tertiary methyls at δH 1.38 and 1.13, one doublet signal for a secondary methyl at δH 1.03 (d, J = 6.8 Hz), an olefinic proton at δH 5.55 (br d, J = 5.5 Hz), as well as four anomeric protons at δH 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 δH 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-1β,3β,21,23,24-pentol] 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. The large coupling constants (3J1,2 > 7 Hz) were consistent with β-configuration for the glucose, galactose, and xylose, while the α-configuration for the rhamnose was deduced by comparing its 13C NMR spectroscopic data for C-3″ (δC 72.4) and C-5″ (δC 69.5) with those reported in the literature [21]. The sequence and binding sites of the sugar units were determined by following HMBC correlations: δH 6.41 (H-1″ of Rha) with δC 76.3 (C-2′ of Glc), δH 4.91 (H-1″′ of Xyl) with δC 88.3 (C-3′ of Glc), δH 4.78 (H-1′ of Glc) with δC 83.9 (C-1 of the aglycone), and δH 5.24 (H-1″″ of Gal) with δC 81.8 (C-24 of the aglycone). Assignment of all proton and carbon resonances was achieved by interpretation of 1H-1H COSY, HSQC, and HMBC spectra. Based on the above information, the structure of paristenoside A (1) was elucidated as 24-O-β-d-galactopyranosyl-(23S,24S,25S)-spirost-5-ene-1β,3β,21,23,24-pentol-1-O-α-l-rhamnopyranosyl-(1 → 2)-[β-d-xylopyranosyl-(1 → 3)]-β-d-glucopyranoside.Table 1

Bottom Line: 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.In addition, the cytotoxicity of the two new saponins was tested.Two new highly oxygenated spirostanol saponins, paristenosides A (1) and B (2), were isolated from the rhizomes of Paris polyphylla var. stenophylla.

View Article: PubMed Central - PubMed

Affiliation: College of Pharmacy and Chemistry, Dali University, Dali, 671000, China.

ABSTRACT
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. 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.

No MeSH data available.