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Spiralosides A-C, Three New C27-Steroidal Glycoalkaloids from the Fruits of Solanum spirale.

Li D, Zhao YL, Qin XJ, Liu L, Yang XW, Chen YY, Wang B, Wei X, Liu YP, Luo XD - Nat Prod Bioprospect (2016)

Bottom Line: Three new C27-steroidal glycoalkaloids, spiralosides A-C (1-3), were obtained from the total alkaloids of Solanum spirale by chromatographic methods.On the basis of spectroscopic evidence, spiralosides A-C were elucidated as (22R,25S)-22,26-epiminocholest-5-ene-3β,16α-diol-N-acetyl-3-O-α-L-rhamnopyranosyl-(1→4)-β-D-glucopyranosyl (1), (22R,25S)-22,26-epiminocholest-5-ene-3β,16α-diol-N-acetyl-3-O-β-D-glucopyranosyl (2), (22R,25S)-22,26-epiminocholest-3β,16α-diol-N-acetyl-3-O-β-D-glucopyranosyl (3), respectively.The total alkaloids of S. spirale have been screened for their antitussive and expectorant effects in intact animal model.

View Article: PubMed Central - PubMed

Affiliation: State Key Laboratory of Phytochemistry and Plant Resources in West China, Kunming Institute of Botany, Chinese Academy of Sciences, Kunming, 650201, China.

ABSTRACT
Three new C27-steroidal glycoalkaloids, spiralosides A-C (1-3), were obtained from the total alkaloids of Solanum spirale by chromatographic methods. On the basis of spectroscopic evidence, spiralosides A-C were elucidated as (22R,25S)-22,26-epiminocholest-5-ene-3β,16α-diol-N-acetyl-3-O-α-L-rhamnopyranosyl-(1→4)-β-D-glucopyranosyl (1), (22R,25S)-22,26-epiminocholest-5-ene-3β,16α-diol-N-acetyl-3-O-β-D-glucopyranosyl (2), (22R,25S)-22,26-epiminocholest-3β,16α-diol-N-acetyl-3-O-β-D-glucopyranosyl (3), respectively. The total alkaloids of S. spirale have been screened for their antitussive and expectorant effects in intact animal model.

No MeSH data available.


Related in: MedlinePlus

The chemical structures of spiralosides A–C (1–3)
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Fig1: The chemical structures of spiralosides A–C (1–3)

Mentions: Compound 1 was obtained as a white, amorphous powder; −46.6 (c 0.03, MeOH). It displayed a positive reaction to Dragendorff’s reagent and gave the molecular formula of C41H67NO12 by HRESIMS at m/z 788.4553 [M+Na]+ (calcd for 788.4561), corresponding to nine degrees of unsaturation. The 1H-, 13C-NMR and DEPT spectra displayed two sugar units on basis of three proton signals at δH 4.36 (1H, d, J = 7.8 Hz), 4.81 (1H, br s), and 1.23 (3H, d, J = 6.2 Hz), two anomeric carbons [δC 102.3 (d), and 102.9 (d)], a methyl group (δC 17.8), a methylene carbon (δC 62.1), and other 8 methines signals between δC 70.6 and δC 79.9. The coupling constant (J = 7.8 Hz) of the anomeric proton at δH 4.36 (1H, d, H-1) indicated the β-configuration of the glucosyl residues [16]. Likewise the other anomeric configuration of the rhamnopyranosyl was confirmed as α-orientated on the basis of the chemical shift values of C-3″ (δC 72.2), C-5″ (δC 70.6) with those of the corresponding carbons of methyl α- and β-rhamnopyranoside [17].The identification of the sugar residues were continued by hydrolysis with 10 % HCl to afford d-glucose and l-rhamnose, which were confirmed by GC chromatographic analysis of their l-cysteine methyl ester-TMS derivates. Besides of two sugar units, 13C-NMR and DEPT spectra also showed 29 carbons, five methyl groups, ten methylenes, ten methines, and four quaternary carbons (Table 1). Comparison of above data with those of capsimine [18] and baikeine [19], pingbeinine [20] showed that the aglycone of 1 was similar to capsimine with exception of an additional acetyl group at δC 22.2 (q) and 172.4 (s) in 1 (Fig. 1). This acetyl group (δC 22.2, q and 172.4, s) was located at N in last ring by correlations of δH 2.08 (3H, s, H-29) with δC 172.4 (s, C-28) and 50.7 (t, C-26), of δH 3.60 (1H, overlap, H-26a), 2.91 (1H, t, J = 12.4 Hz, H-26b), and 4.46 (1H, dt, J = 6.1, 6.0 Hz, H-22) with δC 172.4 (s, C-28). Signal at δH 4.22 (1H, t, J = 7.4 Hz) corresponding to δC 76.3 (t) in its HSQC spectrum showed cross peaks with δC 61.9 (d, C-17), 55.2 (d, C-14), and 37.4 (t, C-15), which suggested that the hydroxyl substitute at C-16. The other oxygenic proton signal at δH 3.53 (1H, m) placed at C-3, which was confirmed by HMBC correlations of δH 1.84 (1H, m, H-1a), 1.03 (1H, d, J = 4.3 Hz, H-1b), 2.38 (1H, dd, J = 2.1, 13.1 Hz, H-4a), and 2.22 (1H, t, J = 12.4 Hz, H-4b) with δC 79.9 (d, C-3) (Fig. 2). The glycositatic position was unambiguously ascribed to be at C-3 from the HMBC correlation of δH 4.36 (1H, d, J = 7.8 Hz, H-1′) with C-3 (δC 79.9). The 1H-1H COSY spectrum of 1 displayed five partial fragments a–e (Fig. 2). The signals of fragments a and b were from δH 4.36 (1H, d, J = 7.8 Hz, H-1′) to δH 4.76 and 3.62 (1H each, H-6′), from δH 4.81 (1H, br s, H-1″) to δH 1.23 (3H, q, J = 7.8 Hz, H-6″), respectively, were further suggested a rhamnose and a glucose appeared. On the basis of δH 4.81 (1H, br s, H-1″) correlating with C-4′ (δC 79.6), the presence of a rhamnopyranosyl (1→4)-glucopyranosyl moiety was deduced (Fig. 2).Table 1


Spiralosides A-C, Three New C27-Steroidal Glycoalkaloids from the Fruits of Solanum spirale.

Li D, Zhao YL, Qin XJ, Liu L, Yang XW, Chen YY, Wang B, Wei X, Liu YP, Luo XD - Nat Prod Bioprospect (2016)

The chemical structures of spiralosides A–C (1–3)
© Copyright Policy - OpenAccess
Related In: Results  -  Collection

License
Show All Figures
getmorefigures.php?uid=PMC4940254&req=5

Fig1: The chemical structures of spiralosides A–C (1–3)
Mentions: Compound 1 was obtained as a white, amorphous powder; −46.6 (c 0.03, MeOH). It displayed a positive reaction to Dragendorff’s reagent and gave the molecular formula of C41H67NO12 by HRESIMS at m/z 788.4553 [M+Na]+ (calcd for 788.4561), corresponding to nine degrees of unsaturation. The 1H-, 13C-NMR and DEPT spectra displayed two sugar units on basis of three proton signals at δH 4.36 (1H, d, J = 7.8 Hz), 4.81 (1H, br s), and 1.23 (3H, d, J = 6.2 Hz), two anomeric carbons [δC 102.3 (d), and 102.9 (d)], a methyl group (δC 17.8), a methylene carbon (δC 62.1), and other 8 methines signals between δC 70.6 and δC 79.9. The coupling constant (J = 7.8 Hz) of the anomeric proton at δH 4.36 (1H, d, H-1) indicated the β-configuration of the glucosyl residues [16]. Likewise the other anomeric configuration of the rhamnopyranosyl was confirmed as α-orientated on the basis of the chemical shift values of C-3″ (δC 72.2), C-5″ (δC 70.6) with those of the corresponding carbons of methyl α- and β-rhamnopyranoside [17].The identification of the sugar residues were continued by hydrolysis with 10 % HCl to afford d-glucose and l-rhamnose, which were confirmed by GC chromatographic analysis of their l-cysteine methyl ester-TMS derivates. Besides of two sugar units, 13C-NMR and DEPT spectra also showed 29 carbons, five methyl groups, ten methylenes, ten methines, and four quaternary carbons (Table 1). Comparison of above data with those of capsimine [18] and baikeine [19], pingbeinine [20] showed that the aglycone of 1 was similar to capsimine with exception of an additional acetyl group at δC 22.2 (q) and 172.4 (s) in 1 (Fig. 1). This acetyl group (δC 22.2, q and 172.4, s) was located at N in last ring by correlations of δH 2.08 (3H, s, H-29) with δC 172.4 (s, C-28) and 50.7 (t, C-26), of δH 3.60 (1H, overlap, H-26a), 2.91 (1H, t, J = 12.4 Hz, H-26b), and 4.46 (1H, dt, J = 6.1, 6.0 Hz, H-22) with δC 172.4 (s, C-28). Signal at δH 4.22 (1H, t, J = 7.4 Hz) corresponding to δC 76.3 (t) in its HSQC spectrum showed cross peaks with δC 61.9 (d, C-17), 55.2 (d, C-14), and 37.4 (t, C-15), which suggested that the hydroxyl substitute at C-16. The other oxygenic proton signal at δH 3.53 (1H, m) placed at C-3, which was confirmed by HMBC correlations of δH 1.84 (1H, m, H-1a), 1.03 (1H, d, J = 4.3 Hz, H-1b), 2.38 (1H, dd, J = 2.1, 13.1 Hz, H-4a), and 2.22 (1H, t, J = 12.4 Hz, H-4b) with δC 79.9 (d, C-3) (Fig. 2). The glycositatic position was unambiguously ascribed to be at C-3 from the HMBC correlation of δH 4.36 (1H, d, J = 7.8 Hz, H-1′) with C-3 (δC 79.9). The 1H-1H COSY spectrum of 1 displayed five partial fragments a–e (Fig. 2). The signals of fragments a and b were from δH 4.36 (1H, d, J = 7.8 Hz, H-1′) to δH 4.76 and 3.62 (1H each, H-6′), from δH 4.81 (1H, br s, H-1″) to δH 1.23 (3H, q, J = 7.8 Hz, H-6″), respectively, were further suggested a rhamnose and a glucose appeared. On the basis of δH 4.81 (1H, br s, H-1″) correlating with C-4′ (δC 79.6), the presence of a rhamnopyranosyl (1→4)-glucopyranosyl moiety was deduced (Fig. 2).Table 1

Bottom Line: Three new C27-steroidal glycoalkaloids, spiralosides A-C (1-3), were obtained from the total alkaloids of Solanum spirale by chromatographic methods.On the basis of spectroscopic evidence, spiralosides A-C were elucidated as (22R,25S)-22,26-epiminocholest-5-ene-3β,16α-diol-N-acetyl-3-O-α-L-rhamnopyranosyl-(1→4)-β-D-glucopyranosyl (1), (22R,25S)-22,26-epiminocholest-5-ene-3β,16α-diol-N-acetyl-3-O-β-D-glucopyranosyl (2), (22R,25S)-22,26-epiminocholest-3β,16α-diol-N-acetyl-3-O-β-D-glucopyranosyl (3), respectively.The total alkaloids of S. spirale have been screened for their antitussive and expectorant effects in intact animal model.

View Article: PubMed Central - PubMed

Affiliation: State Key Laboratory of Phytochemistry and Plant Resources in West China, Kunming Institute of Botany, Chinese Academy of Sciences, Kunming, 650201, China.

ABSTRACT
Three new C27-steroidal glycoalkaloids, spiralosides A-C (1-3), were obtained from the total alkaloids of Solanum spirale by chromatographic methods. On the basis of spectroscopic evidence, spiralosides A-C were elucidated as (22R,25S)-22,26-epiminocholest-5-ene-3β,16α-diol-N-acetyl-3-O-α-L-rhamnopyranosyl-(1→4)-β-D-glucopyranosyl (1), (22R,25S)-22,26-epiminocholest-5-ene-3β,16α-diol-N-acetyl-3-O-β-D-glucopyranosyl (2), (22R,25S)-22,26-epiminocholest-3β,16α-diol-N-acetyl-3-O-β-D-glucopyranosyl (3), respectively. The total alkaloids of S. spirale have been screened for their antitussive and expectorant effects in intact animal model.

No MeSH data available.


Related in: MedlinePlus