Chem. Pharm. Bull. 63, 388–392 (2015)

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Catunarosides I–L, Four New Triterpenoid Saponins from the Stem Bark of Catunaregam spinosa Jun Li,a,b Xuan Huang,a Xiao-Hong Jiang,a Qi-Feng Zhu,a Yun Yang,a and Guang-Chun Gao*,a a

 Key Laboratory of Natural Medicine and Health Food R & D Technology, College of Medicine, Jiaxing University; No. 118, JiaHang Road, Jiaxing 314001, P. R. China: and b Jiaxing Academy of Agricultural Sciences; ShuangQiao Road, Jiaxing 314016, P. R. China. Received January 19, 2015; accepted March 3, 2015; advance publication released online March 12, 2015 Four new triterpenoid saponins, Catunaroside I [3-O-β- D -glucopyranosyl-(1→3)-β- D -glucopyranosylarjunic acid 28-O-β- D -glucopyranoside] (1), Catunaroside J [3-O-β- D -glucopyranosyl-(1→2)-[β- D glucopyranosyl-(1→3)]-β- D -glucopyranosyl-arjunic acid 28-O-β- D -glucopyranoside] (2), Catunaroside K [3-O-β- D -glucopyranosyl-(1→2)-[β- D -glucopyranosyl-(1→3)]-β- D -glucopyranosyl-tormentic acid] (3), and Catunaroside L [3-O-β- D -glucopyranosyl-(1→2)-[β- D -glucopyranosyl-(1→3)]-β- D -glucopyranosyl-pomolic acid] (4), and two known triterpenoid saponin Arjunetoside (5) and Randiasaponin VII (6), were isolated from the stem bark of Catunaregam spinosa. Their structures were elucidated on the basis of their spectral data and chemical evidence. Key words gam spinosa

Catunaroside I; Catunaroside J; Catunaroside K; Catunaroside L; triterpenoid saponin; Catunare-

Catunaregam spinosa T. (Rubiaceae), distributed in tropical and semitropical areas, was known as a folk medicine in India and Brazil for its antispasmodic, antidysenteric, anti-inflammatory, immunomodulatory and antifertility properties.1–4) Many phytochemical research has been done on this plant, and coumarin glucosides,5) iridoid glucosides,1) and triterpenoid saponins4,6,7) were found. Our previous investigations on this plant had led to the isolation of iridioid,8) norneolignans,9) triterpenoid saponins.10,11) In continuation of our studies on the plants, four new triterpenoid saponins, Catunarosides I–L, together with Arjunetoside and Randiasaponin VII, were isolated from the n-BuOH extract of its stem bark by preparative HPLC. The isolation and structure determination of those triterpenoid saponins were elucidated in this paper.

Results and Discussion

Compound 1 was obtained as a colorless amorphous powder. The molecular formula C48H78O20 was determined by a combination of NMR spectra and high resolution-electrospray ionization (HR-ESI)-MS which exhibited a molecular ion peak at m/z: 997.4980 [M+Na]+ (Calcd for C48H78O20Na: 977.4984). On acid hydrolysis, 1 afforded only glucose as sugar moiety that was identical to an authentic sample by Silica gel TLC. The IR spectrum showed absorption bands at 3417 cm−1 (OH), 1726 cm−1 (C=O), 1643 cm−1 (C=C). The 13 C-NMR spectrum exhibited 48 signals, of which 30 were assigned to the aglycone moiety and 18 to the sugars. In the 1 H-NMR spectrum, seven methyl protons (δ 1.37, 1.05, 0.96, 1.14, 1.63, 1.14 and 0.98 ppm; each 3H, s), one olefinic methine proton (δ 5.49, br s), and three anomeric protons (δ 4.91, d, 8.0 Hz; 5.29, d, 7.5 Hz; 6.38, d, 8.0 Hz) were observed. The 13 C-NMR spectrum also showed seven methyl carbons at δ 28.4, 18.0, 16.6, 17.6, 24.9, 28.7 and 24.6 ppm, two olefinic carbons at δ 122.9 and 144.3 ppm, three oxygenated methine carbons at δ 66.6, 95.7 and 81.0 ppm, and three anomeric carbons at δ 106.0, 105.9 and 95.9. Based on the above data, it was deduced that 1 was an olean-12-ene type triterpenoid

glycoside with three units of glucose. The comparison of 1 H- and 13C-NMR spectrum data of aglycone part of 1 with that of arjunic acid12) indicated that compound 1 possessed a 2α,3β,19α-trihydroxyolean-12-ene-28-oic acidic aglycone. The chemical shifts of C-3 (δ 95.7) and C-28 (δ 177.2)13) implied that 1 was a 3,28-bisdesmosidic glycoside. This hypothesis was also in agreement with the relatively downfield shifts of anomeric protons (δ 4.91, 6.38 ppm) and the corresponding upfield shifts of anomeric carbons (δ 106.0, 95.9 ppm). In the heteronuclear multiple bond connectivity (HMBC) spectrum, significant correlations between signals at δ 4.91(H-1′) and δ 95.7 (C-3), δ 5.29 (H-1″) and δ 88.9 (C-3′), and δ 6.37 (H-1⁗) and δ 177.2 (C-28) were observed. The β-anomeric configurations of glucose units were determined by the relatively large 3J H1, H2 coupling constants (7.5–8.0 Hz). Considering above information compound 1 was elucidated as 3-O-β-D glucopyranosyl-(1→3)-β-D -glucopyranosyl-arjunic acid 28-Oβ-D -glucopyranoside (Fig. 1). Compound 2, a colorless amorphous powder, was analyzed to have the molecular formula of C54H88O25 by its HR-ESI-MS spectrum (m/z: 1159.5563 [M+Na]+). Acid hydrolysis of 2 afforded glucose as the only sugar unit. The 13C-NMR spectrum revealed 54 signals, of which 30 were assigned to the aglycone and 24 to the sugars. The 1H-NMR spectrum showed seven methyl protons (δ 1.28, 1.18, 0.92, 1.12, 1.60, 1.14, 0.97 ppm; each 3H, s), one olefinic methine proton (δ 5.47, br s), and four sugar anomeric protons (δ 4.82, d, J=7.5 Hz; 5.38, d, J=7.5 Hz; 5.85, d, J=7.5 Hz; 6.37, d, J=8.0 Hz). The signals of seven methyl carbons at δ 28.2, 17.6, 16.7, 17.7, 24.9, 28.7 and 24.7 ppm, two olefinic methine carbons at δ 123.1 and 144.3 ppm, four sugar carbons at δ 104.5, 104.6, 103.6 and 95.9 ppm, and two carbons at δ 177.3 and 96.5 ppm linked to glycan part were also observed in the 13C-NMR spectrum. The above evidence revealed that 2 was a bisdesmosidic glycoside. And the aglycone part of this compound was determined as 2α,3β,19α-trihydroxyolean-12-ene-28-oic acid comparing the 1H- and 13C-NMR signals of 2 with those of

 To whom correspondence should be addressed.  e-mail: [email protected] *  © 2015 The Pharmaceutical Society of Japan

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Fig. 1.

Structures of Compounds 1–6

3-O-β- D -glucopyranosyl-2α,3β,19α-trihydroxyolean-12-en-28oic acid-28-O-β-D -glucopyranoside.12) According to the 1Hand 13C-NMR signals, the aglycone and sugar moieties of 2 were assigned based on the two dimensional (2D)-NMR spectra, and the exact glycosidic linkages were unambiguously confirmed by the following HMBC correlations between H-1⁗ (δ 6.37) of a glucose and C-28 (δ 177.3) of aglycone part; H-1′ (δ 4.82) of the inner glucose and C-3 (δ 96.5) of aglycone part; H-1″ (δ 5.38) of the 3′-O-glucose and C-3′ (δ 88.9) of inner glucose; H-1‴ (δ 5.85) of the 2′-O-glucose and C-2′ (δ 78.3) of inner glucose. The β-anomeric configurations of the glucose units were established by its 3J H1, H2 coupling constants (7.5–8.0 Hz). On the basis of above results compound 2, named as Catunaroside J, was determined as 3-O-β-D -glucopyranosyl-(1→2)-[β- D -glucopyranosyl-(1→3)]-β- D -glucopyranosylarjunic acid 28-O-β-D -glucopyranoside (Fig. 1). Compound 3, also an amorphous powder, has the molecular formula of C48H78O20 as indicated from its HR-ESI-MS (m/z 997.5001 [M+Na]+) spectrum. Acid hydrolysis implied that compound 3 only contained glucose by comparing Rf value with that of authentic sample. The 13C-NMR spectrum revealed 48 signals, of which 30 were assigned to the aglycone and 18 to the sugars. The 1H-NMR spectrum exhibited signals for seven methyl protons (δ 1.28 s, 1.17 s, 0.88 s, 1.06 s, 1.70 s, 1.43 s and 1.12 d, J=6.5 Hz), one olefinic methine proton (δ 5.56, br s) and three sugar anomeric protons (δ 4.82, d, J=7.5 Hz; 5.38, d, J=7.5 Hz; 5.85, d, J=8.0 Hz). In the 13 C-NMR spectrum, the signals of seven methyl carbons at δ 28.2, 17.8, 16.6, 17.2, 24.7, 27.1 and 16.8 ppm, two olefinic methine carbons at δ 128.0 and 139.9 ppm, three sugar carbons at δ 104.4, 104.7 and 103.6 ppm were observed. The above evidence suggested that 3 may be an urs-12-ene type triterpenoid glycoside with three glucose residue. The NMR characteristic carbon signals (δ 66.6, 72.8 ppm) and proton signal (δ 1.12 d, J=6.5 Hz) suggested that the aglycone part was tormentic acid, then it was proved by comparing with NMR data from reference.14) The carbon signals in 13C-NMR spectrum at δ 96.4 (C-3) and 180.6 (C-28) inferred compound 3 was a 3-Omonodesmosidic saponin. The β-anomeric configurations of the glucose units were established according to its 3J H1, H2 coupling constants (7.5–8.0 Hz). The sequence of the glycan part connected to C-3 of the aglycone was deduced from the

following HMBC correlations: H-1′ (δ 4.82) of inner glucose with C-3 (δ 96.4) of aglycone part, H-1″ (δ 5.38) of 3′-O-glucose with C-3′ (δ 88.9), and H-1‴ (δ 5.85) of 2′-O-glucose with C-2′ (δ 78.3). From the above evidence, compound 3 was identified as 3-O-β-D -glucopyranosyl-(1→2)-[β-D -glucopyranosyl(1→3)]-β-D -glucopyranosyl-tormentic acid, named as Catunaroside K (Fig. 1). Compound 4, obtained as an amorphous powder, was deduced to have the molecular formula C48H78O19 as indicated from HR-ESI-MS (m/z: 981.5080 [M+Na]+) data. The IR spectrum showed the presence of C=O group at 1741 cm−1 and a C=C group at 1659 cm−1. The 1H-NMR spectrum revealed signals due to seven methyl protons (δ 1.25 s, 1.20 s, 0.80 s, 1.02 s, 1.74 s, 1.45 s, and 1.07 d, J=7.0 Hz), an olefinic proton (δ 5.59 br s) and three anomeric protons (δ 4.84, d, J=7.6 Hz; 5.38, d, J=7.6 Hz; 5.73, d, J=7.6 Hz). The corresponding signals at δ 28.0, 16.7, 15.5, 17.2, 24.7, 27.2 and 16.8 (seven methyl carbons) ppm, δ 128.0 and 140.0 (an olefinic carbons) ppm, and δ 105.1, 104.7 and 103.8 (three anomeric carbons) ppm were also observed in 13C-NMR spectrum. Based on above observations, the NMR signals of 4 were in good agreement with those of sibiricasaponins B (pomolic acid 3-O-(3-O-sulfo)-α-Larabinopyranoside)15) except for the signals of 3-O-substituted sugar moieties. Acid hydrolysis of 4 showed the only existence of glucose. The exact sugar arrangement was determined to be 3-O-β-D -glucopyranosyl-(1→2)-[β-D -glucopyranosyl(1→3)]-β-D -glucose according to the reported NMR data of aralia saponin V.16) The conclusion was then proved by the HMBC correlations between signals at δ 4.84 (H-1′) of inner glucose and δ 96.4 (C-3) of aglycone part, δ 5.38 (H-1″) of 3′-O-glucose and δ 88.6 (C-3′), and δ 5.73 (H-1‴) of 2′-Oglucose and δ 79.3 (C-2′). Thus compound 4 was elucidated as 3-O-β- D -glucopyranosyl-(1→2)-[β- D -glucopyranosyl-(1→3)]β-D -glucopyranosyl-pomolic acid, named as Catunaroside L (Fig. 1). Compounds 5 and 6 were elucidated as Arjunetoside and Randiasaponin VII separately by comparison of their spectrum data with data reported in the literatures (IR, MS, 1Hand 13C-NMR).12,17)

Experimental

General Silica gel (100–200 mesh and 200–300 mesh,

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Qingdao Haiyang Chemical Co., Ltd.), Macroporous resin D101, Lichroprep RP-18 (Merck) and Sephadex LH-20 (Pharmacia) were used for column chromatography. TLC was performed on precoated silica gel 60 F254 plates (Qingdao Haiyang Chemical Co., Ltd.), and detection was achieved by 10% H2SO4 –EtOH. Semipreparative HPLC was carried out using an octadecyl silica (ODS) column (YMC-Pack ODS-5-A, 250×10 mm i.d., 5 µm; YMC) on a Waters-600 HPLC system equipped with a Waters-996 photodiode array detector. IR spectra were measured with a Bruker EQUINOX55 infrared spectrometer. 1H- and 13C-NMR spectra were recorded on a Bruker DRX-500 spectrometer (SiMe4 as internal standard). MS were obtained on MDS SCIEX API 2000 LC/MS/MS instrument for ESI and Bruker BioTOF Q spectrometer for HR-ESI. GC analysis were done on Agilent 1200 with HP-5 column (0.32 mm×30 mm, 0.25 µm) and 1200 FID detector. Plant Material The stem bark of C. spinosa, collected Table 1.

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from Sanya, Hainan Province, P. R. China in February 2006, was identified by professor Si Zhang (South China Sea Institute of Oceanology, Chinese Academy of Sciences). And a voucher specimen has been deposited in the South China Sea Institute of Oceanology, Chinese Academy of Sciences (accession number: GKLMMM020). Extraction and Isolation The n-BuOH extract (170 g), obtained from air-dried and powered plant material using method reported previously,9) was passed through a macroporous resin (D101) column eluted with H2O and EtOH–H2O (30 : 70, 60 : 40, 95 : 5) in turn. The EtOH–H2O (60 : 40) eluted portion (35 g) from n-BuOH soluble fraction was subjected to silica gel CC eluted with CHCl3–MeOH (90 : 10–50 : 50) to give fractions a–f. Fraction b was separated by Sephadex LH-20 eluting with MeOH, then fractions 2–10 and 11–20 were purified by preparative HPLC eluting with MeOH–H2O (45 : 55) and MeOH–H2O (50 : 50) to obtain compounds 1 (15 mg), 5 (12 mg)

Selected 1H-NMR Spectroscopic Data of 1–4 in Pyridine-d5 (500, 125 MHz)

Position

1

2 3 12 18 19 23 24 25 26 27 29 30 3-O1′ 2′ 3′ 4′ 5′ 6′ 3′-O1″ 2″ 3″ 4″ 5″ 6″ 2′-O1‴ 2‴ 3‴ 4‴ 5‴ 6‴ 28-O1⁗ 2⁗ 3⁗ 4⁗ 5⁗ 6⁗

4.00 3.24 5.49 3.53 3.57 1.37 1.05 0.96 1.14 1.63 1.14 0.98

2 (d, 9.5) (br s) (br s) (br s) (s) (s) (s) (s) (s) (s) (s)

3.94 3.14 5.47 3.51 3.55 1.28 1.18 0.92 1.12 1.60 1.14 0.97

3 (d, 9.0) (br s) (br s) (br s) (s) (s) (s) (s) (s) (s) (s)

4

3.93 3.16 (d, 9.0) 5.54 (br s) 3.03 (br s)

2.04 3.28 5.59 3.05

m (dd, 4.4, 11.5) (br s) (br s)

1.28 1.17 0.88 1.06 1.70 1.43 1.12

1.25 1.20 0.80 1.02 1.74 1.45 1.07

(s) (s) (s) (s) (s) (s) (d, 7.0)

(s) (s) (s) (s) (s) (s) (d, 6.5)

4.91 (d, 8.0) 4.09 4.23 4.10 4.22 4.42, 4.53

4.82 (d, 7.5) 4.42 4.26 4.00 3.93 4.31, 4.48

4.82 (d, 7.5) 4.41 4.27 3.99 3.92 4.31, 4.49

4.84 (d, 7.6) 4.42 4.25 4.01 3.92 4.30, 4.48

5.29 (d, 7.5) 4.12 4.30 4.19 4.25 4.42, 4.53

5.38 (d, 7.5) 4.21 4.22 4.16 4.28 4.43, 4.53

5.38 (d, 7.5) 4.32 4.23 4.16 4.31 4.47, 4.54

5.38 (d, 7.6) 4.28 4.25 4.17 4.30 4.42, 4.55

5.85 (d, 7.5) 4.06 4.15 3.93 3.92 4.18, 4.26

5.85 (d, 8.0) 4.06 4.16 3.92 3.91 4.18, 4.26

5.73 (d, 7.6) 4.04 4.15 3.98 3.90 4.17, 4.26

6.38 (d, 8.0) 4.23 4.04 4.38 4.37 4.25, 4.32

Overlapped proton signals are reported without designated multiplicity.

6.37 (d, 8.0) 4.22 4.05 4.36 4.30 4.43, 4.53

Chem. Pharm. Bull. Vol. 63, No. 5 (2015)391

and 6 (12 mg) separately; Fraction f was rechromatographed to silica gel CC eluted with CHCl3–MeOH–H2O (80 : 20 : 5), then fraction 12 was purified by preparative HPLC using MeOH– H2O (48 : 52) to yield compound 2 (21 mg); The EtOH–H2O (95 : 5) eluted portion (10 g) was subjected to silica gel CC eluted with CHCl3–MeOH (98 : 2–50 : 50) to give fractions A–G. Fraction E was purified by sephadex LH-20 (MeOH), then separated by preparative HPLC to obtain compound 3 (19 mg) using MeOH–H2O (65 : 35) and compound 4 (10 mg) using MeOH–H2O (68 : 32). Catunaroside I (1) Colorless amorphous powder, [α]D20 +12.7 (c=0.5, MeOH). IR (KBr, cm−1) ν max: 3417, 1726, 1643. 1 H-NMR (500 MHz, pyridine-d5) and 13C-NMR (125 MHz, pyridine-d5) data: see Tables 1 and 2. ESI-MS m/z: 997 [M+Na]+, 1013 [M+K]+. HR-ESI-MS m/z: 997.4980 [M+Na]+ (Calcd for C48H78O20Na, 997.4984). Catunaroside J (2) Colorless amorphous powder, [α]D20 +39.1 (c=0.3, MeOH). IR (KBr, cm−1) ν max: 3420, 1735, 1640. 1H-NMR (500 MHz, pyridine-d5) and 13C-NMR (125 MHz, pyridine-d5) data: see Tables 1 and 2. ESI-MS m/z: 1159[M+Na]+. HR-ESI-MS m/z: 1159.5563 [M+Na]+ (Calcd for C54H88O25Na, 1159.5512). Catunaroside K (3) Colorless amorphous powder, [α]D20 +27.8 (c=0.3, MeOH). IR (KBr, cm−1) ν max: 3419, 1730, 1643. 1 H-NMR (500 MHz, pyridine-d5) and 13C-NMR (125 MHz, pyridine-d5) data: see Tables 1 and 2. ESI-MS m/z: 997 [M+Na]+, 1013 [M+K]+. HR-ESI-MS m/z: 997.5001 [M+Na]+ Table 2.

13

C-NMR Spectroscopic Data of 1–4 in Pyridine-d5 (500, 125 MHz)

Position 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30

(Calcd for C48H78O20Na, 997.4984). Catunaroside L (4) Colorless amorphous powder, [α]D20 +40.3 (c=0.5, MeOH). IR (KBr, cm−1) ν max: 3422, 1741, 1659. 1 H-NMR (500 MHz, pyridine-d5) and 13C-NMR (125 MHz, pyridine-d5) data: see Tables 1 and 2. ESI-MS m/z: 981 [M+Na]+, 997 [M+K]+. HR-ESI-MS m/z: 981.5080 [M+Na]+ (Calcd for C48H78O19Na, 981.5035). Acid Hydrolysis of 1–6 and Determination of the Absolute Configuration of Glucoses Acid hydrolysis of compounds 1–6 was done using the method reported previously.10) The sugars were identified by comparing of the Rf value with that of glucose on TLC plate eluted with CHCl3–MeOH–H2O (8 : 7 : 1) solvent system, visualized with ethanol–10% H2SO4 spraying and then heating. The sugar residue and the authentic samples of D -glucose and L-glucose were dissolved in 0.2 mL anhydrous pyridine and L-cysteine methyl ester hydrochloride, then warmed at 60°C for 1 h. The trimethylsilylation reagent trimethylsilylimidazole was added, followed by warming at 60°C for 1 h. After drying the residue was partition between H2O and cyclohexane. The cyclohexane layer was analyzed by GC using a HP-5 column. The temperatures of the injector and detector were 270 and 280°C, respectively. A temperature gradient system used for the oven was started with 160°C for 4 min and increased up to 240°C at a rate of 6°C/min. The retention time (24.15 min) of sugar residue were the same with that of D -glucose.

1 47.0 66.6 95.7 40.7 55.7 18.7 33.0 40.2 48.2 38.0 24.2 122.9 144.3 42.2 29.0 28.0 46.5 44.6 81.0 35.5 28.9 33.1 28.4 18.0 16.6 17.6 24.9 177.2 28.7 24.6

2 47.1 66.6 96.5 41.0 55.8 18.8 33.1 40.2 48.3 38.0 24.2 123.1 144.3 42.2 29.0 28.0 46.5 44.6 81.1 35.6 29.0 33.2 28.2 17.6 16.7 17.7 24.9 177.3 28.7 24.7

3 47.4 66.6 96.4 40.3 55.7 18.7 33.4 40.9 47.7 37.8 24.0 128.0 139.9 42.4 29.3 26.4 48.3 54.6 72.8 42.1 26.9 38.5 28.2 17.8 16.6 17.2 24.7 180.6 27.1 16.8

4 38.8 26.4 89.5 39.6 55.9 18.6 33.5 40.3 47.7 36.9 24.0 128.0 140.0 42.4 29.3 26.4 48.3 54.6 72.7 42.1 27.0 38.5 28.0 16.7 15.5 17.2 24.7 180.7 27.2 16.8

Position 3-O1′ 2′ 3′ 4′ 5′ 6′ 3′-O1″ 2″ 3″ 4″ 5″ 6″ 2′-O1‴ 2‴ 3‴ 4‴ 5‴ 6‴ 28-O1⁗ 2⁗ 3⁗ 4⁗ 5⁗ 6⁗

1

2

3

4

106.0 75.5 88.8 69.7 78.1 62.2

104.5 78.3 88.9 69.9 78.0 63.5

104.4 78.3 88.9 69.9 78.0 63.5

105.1 79.3 88.6 70.1 77.7 63.4

105.9 74.3 78.7 71.6 78.3 62.2

104.6 74.2 78.7 71.6 78.8 62.2

104.7 76.2 78.7 71.6 78.8 62.2

104.7 76.4 78.6 71.6 78.6 62.6

103.6 75.5 78.6 72.8 77.9 62.4

103.6 75.5 78.6 72.7 77.9 62.3

103.8 75.4 78.6 72.7 77.8 62.4

95.9 74.1 78.9 71.1 79.3 62.5

95.9 74.2 79.0 71.1 79.3 62.2

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Acknowledgments This work was financially supported by the Grant of the 12th Five-year Plan for University Key Academic Subject (Pharmacology), Zhejiang Province, CHINA, the Science and Technology Program of Jiaxing (2013AY21047) and the 2011 Annual Jiaxing Key Science and Technology Innovation Team. Conflict of Interest interest.

References

The authors declare no conflict of

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Catunarosides I-L, four new triterpenoid saponins from the stem bark of Catunaregam spinosa.

Four new triterpenoid saponins, Catunaroside I [3-O-β-D-glucopyranosyl-(1→3)-β-D-glucopyranosyl-arjunic acid 28-O-β-D-glucopyranoside] (1), Catunarosi...
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