毛冬青化学成分的研究II: 毛冬青皂苷甲的化学结构

从毛冬青的根皮中分得一种新的三萜皂苷,命名为毛冬青皂苷甲,经^1H NMR、^1^3C NMR、MS、IR、UV和化学转化产物的研究,推定它为3β,19α-二羟基-乌索-12-烯-24,28-二羧酸-28-β-D-葡萄吡喃糖基酯.     

New triterpenoid saponins from Stelmatocrypton khasianum

Four new triterpenoid saponins, designated as stelmatotriterpenosides E-H (1-4), together with three known compounds, asterbatanoside B (5), 2alpha,3beta,19alpha,23-tetrahydroxy-olean-12-en-28-oic acid-3-O-beta-D-glucopyranosyl-28-O-beta-D-glucopyranosyl ester (6) and 2alpha,3beta,19alpha,23-tetrahydroxy-urs-12-en-28-oic acid-3-O-beta-D-glucopyranosyl-28-O-beta-D-glucopyranosyl ester (7), were isolated from the stems of Stelmatocrypton khasianum. On the basis of chemical and spectral evidence, the structures of 1-4 were established as 2alpha,3beta,23-trihydroxy-olean-12-en-28-oic acid-3-O-beta-D-glucopyranosyl-28-O-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl ester (1), 2alpha,3beta,23-trihydroxy-urs-12-en-28-oic acid-3-O-beta-D-glucopyranosyl-28-O-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl ester (2), 2alpha,3beta,19alpha-trihydroxy-urs-12-en-28-oic acid-3-O-beta-D-glucopyranosyl-28-O-beta-D-glucopyranosyl-(1-->2)-beta-D-glucopyranosyl ester (3), and 2beta,3beta,19alpha-trihydroxy-urs-12-en-24,28-dioic acid-24-O-beta-D-glucopyranosyl-28-O-beta-D-glucopyranosyl diester (4).     

Lupane-triterpene carboxylic acids from the leaves of Acanthopanax trifoliatus

Two new lupane-triterpene carboxylic acids, called acantrifoic acid A (1) and acantrifoside C (2) have been isolated from the leaves of Acanthopanax trifoliatus. Based on extensive 1D and 2D NMR spectroscopic data, their chemical structures were determined as 3 alpha-acetoxy-30-hydroxylup-20(29)-ene-23,28-dioic acid and 3 alpha-acetoxy-30-hydroxylup-20(29)-ene-23,28-dioic acid 28-O-alpha-L-rhamnopyranosyl-(1-->4)-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl ester.     

New oleanene glycosides from the leaves of Acanthopanax japonicus

The structures of 6 new oleanene glycosides (1--6) isolated from the leaves of Acanthopanax japonicus FRANCH et. SAVART (Araliaceae) were elucidated by mass, 1D, and 2D NMR spectroscopy. The structures of 1--6 were established as 28-O-[alpha-L-rhamnopyranosyl-(1-->4)-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl] ester of 3beta,23-dihydroxy-olean-12-en-28,29-dioic acid, 3beta,30-dihydroxy-olean-12-en-23,28-dioic acid, 3beta,29-dihydroxy-olean-12-en-23,28-dioic acid (=dianic aicd), 3beta-dihydroxy-olean-12-en-23,28-dioic acid (=gypsogenic acid), 3beta,29-dihydroxy-23-oxo-olean-12-en-28-oic acid, and 3beta-hydroxy-23-oxo-olean-12-en-28,29-dioic acid, designated acanjaposide D (1), E (2), F (3), G (4), H (5), and I (6), respectively.     

New terpenoids from Stachys parviflora Benth

Two new triterpenoidal saponins were isolated from the n-butanolic extract of Stachys parviflora (Lamiaceae). Their structures were elucidated on the basis of spectral data as stachyssaponin A; 3beta, 15alpha, 19alpha, 21beta, 22alpha-pentahydroxyolean-12-ene-28-oic acid 3-O-{alpha-L-rhamnopyranosyl-(1 --> 3)-beta-D-glucopyranoside}-22-O-{alpha-L-arabinofuranosyl-(1 --> 3)-beta-D-glucopyranoside} (1) and stachyssaponin B; 2beta, 3beta, 15alpha, 21beta-tetrahydroxyolean-12-ene-28-oic acid 2-O-[alpha-L-arabinofuranoside]-3, 21-bis-O-[beta-D-glucopyranoside] (2).     

Complete 1H and 13C NMR assignments of three new polyhydroxylated sterols from the South China Sea gorgonian Subergorgia suberosa

Three new polyhydroxylated sterols, 3beta,6alpha,11,20beta,24-pentahydroxy- 9,11-seco-5alpha-24-ethylcholest-7,28-diene-9-one (1), 3-(1',2'-ethandiol)-24- methylcholest-8(9),22E-diene-3beta,5alpha,6alpha,7alpha,11alpha-pentaol (2), 24-methylcholest-7,22 E-diene-3beta,5alpha,6beta,25-tetraol (3) together with five known sterols, were isolated from the EtOH/CH2Cl2 extract of the South China Sea gorgonian Subergorgia suberosa. The complete assignments of the 1H and 13C NMR chemical shifts for these new compounds were achieved by means of 1D and 2D NMR techniques, including HSQC, HMBC, 1H--1H COSY, and NOESY spectra.     

Glycosides from the leaves of Ilex hylonoma

Two new triterpenoid saponins, hylonosides I-II (1,2) have been isolated along with one known flavonoid glycoside (3) from the methanol extract of leaves of Ilex hylonoma. The structures were elucidated by ID and 2D NMR experiments, including 1H-1H COSY, TOCSY, NOESY, HMQC, and HMBC methods. Two new compounds were characterized as 3-O-beta-D-glucopyranosyl-(1 --> 4)-beta-D-glucuronopyranosyl pomolic acid-28-O-beta-D-glucopyranoside (1), 3-O-beta-D-glucopyranosyl-(1 --> 4)-beta-D-glucopyranosyl-(1 --> 2)-beta-D-glucuronopyranosyl pomolic acid-28-O-beta-D-glucopyranoside (2).     

New leishmanicidal physalins from Physalis minima

Two new physalins, 16,24-cyclo-13,14-secoergosta-2-ene-18,26-dioic acid-14 : 17,14 : 27-diepoxy-11beta,13,20,22-tetrahydroxy-5alpha-methoxy-1,15-dioxo-gamma-lactone delta-lactone (1), and 16,24-cyclo-13,14-secoergosta-2-ene-18,26-dioic acid-14 : 17,14 : 27-diepoxy-5alpha,11beta,13,20,22-pentahydroxy-1,6,15-trioxo-gamma-lactone delta-lactone (2), have been isolated from the whole plant of Physalis minima Linn. (var. indica). Their structures were deduced on the basis of spectroscopic analysis. Both of these compounds have shown potent leishmanicidal activity against the promastigotes of Leishmania major.     

Six new dammarane-type triterpene saponins from the leaves of Panax ginseng

Six new minor saponins, together with known ginsenosides, were isolated from the leaves of Panax ginseng. The new saponins were named as ginsenoside-Rh5, -Rh6, -Rh7 -Rh8, -Rh9 and -Rg7, and their structures were elucidated on the basis of chemical and physicochemical evidence to be as follows: ginsenoside-Rh5: 3beta,6alpha,12beta,24zeta-tetrahydroxy-dammar-20(22),25-diene 6-O-beta-D-glucopyranoside (1), -Rh6: 3beta,6alpha12beta,20(S)-tetrahydroxy-25-hydroperoxy-dammar-23-ene 20-O-beta-D-glucopyranoside (2), -Rh7: 3beta,7beta,12beta,20(S)-tetrahydroxy-dammar-5,24-diene 20-O-beta-D-glucopyranoside (3), -Rh8: 3beta,6alpha,20(S)-trihydroxy-dammar-24-ene-12-one 20-O-beta-D-glucopyranoside (4), -Rh9: 3beta,6alpha,20(S)-trihydroxy-12beta,23-epoxy-dammar-24-ene 20-O-beta-D-glucopyranoside (5) and -Rg7: 3-O-beta-D-glucopyranosyl 3beta,12beta,20(S),24(R)-tetrahydroxy-dammar-25-ene 20-O-beta-D-glucopyranoside (6).     

Chemical constituents of the aerial parts of Kalidium foliatum

Studies on the chemical constituents of the aerial parts of Kalidium foliatum have led to the isolation of three new and one known compounds. The structures of new constituents have been elucidated through spectral studies including 2D-NMR experiments (HMQC, HMBC, COSY, NOESY and J-resolved) and MS/MS fragmentation using Q-TOF mass spectrometer equipped with an ESI source as kalidiumoside C (=3beta-hydroxy-29-methylmalonoxy-olean-12-en-23,28-dioic acid-23-methyl-28-beta-D-glucopyranosyl ester; 1), kalidiunin (=3beta,23,29-trihydroxy-olean-12-en-28-methyl-oate; 2) and kalidiumoside D (=3beta,23,29-trihydroxyolean-12-en-28-oic acid-beta-D-glucopyranosyl ester; 3). The known compound was identified as 3beta,23,29-trihydroxy-olean-12-en-28-oic acid 4) through comparison of its spectral data with those reported in literature. Acid hydrolysis of both 2 and 3 yielded the known compound 4 providing a conclusive evidence of the proposed structures.     

Complete assignments of 1H and 13C NMR spectral data for three polyhydroxylated 12-ursen-type triterpenoids from Dischidia esquirolii

The complete assignments of all the (1)H and (13)C NMR signals of three polyhydroxylated 12-ursen-type triterpenes, 6beta,19alpha,22alpha-trihydroxyurs-12-en-3-oxo-28-oic acid (1), 3beta,6alpha,19alpha,23-tetrahydroxyurs-12-en-28- oic acid (2) and 3beta,6beta,19alpha,23-tetrahydroxyurs-12-en-28-oic acid (3), were carried out by means of homo- and hetero-nuclear two-dimensional NMR experiments. Compounds 1-3 were isolated from the aerial parts of Dischidia esquirolii. Of them, 1 and 2 were identified as new polyhydroxylated ursolic acid derivatives. Compound 2 is the C-6 hydroxyl epimer of 3, which was isolated first from Adina rubella, and its structure is revised in this paper.     

Five new bidesmoside triterpenoid saponins from Stauntonia chinensis

Eleven triterpenoid saponins (1-11) were isolated from Stauntonia chinensis DC. (Lardizabalaceae), including five new compounds, yemuoside YM(21-25) (1-3, 6, 7) structures of which were elucidated by chemical methods and a combination of MS, 1D- and 2D- NMR experiments including DEPT, (1)H--(1)H COSY, HSQC, HMBC, TOCSY, and NOESY as 3-O-alpha-L-arabinopyranosyl-(1 --> 3)-[alpha-L-rhamnopyranosyl-(1 --> 2)-]alpha-L-arabinopyranosyl-akebonicacid-28-O-alpha-L-rhamnopyranosyl-(1 --> 4)-beta-D-glucopyranosyl-(1 --> 6)-beta-D-glucopyranosyl ester (1), 3-O-beta-D-xylopyranosyl-(1 --> 3)-alpha-L-rhamnopyranosyl-(1 --> 2)-alpha-L-arabinopyranosyl-akebonic acid-28-O-alpha-L-rhamnopyranosyl-(1 --> 4)-beta-D-glucopyranosyl-(1 --> 6)-beta-D-glucopyranosyl ester (2), 3-O-beta-D-glucopyranosyl-(1 --> 3)-alpha-L-arabinopyranosyl-akebonic acid-28-O-alpha-L-rhamnopyranosyl-(1 --> 4)-beta-D-glucopyranosyl-(1 --> 6)-beta-D-glucopyranosyl ester (3), 3-O-alpha-L-arabinopyranosyl-(1 --> 3)-[alpha-L-rhamnopyranosyl-(1 --> 2)-]alpha-L-arabinopyranosyl-akebonic acid-28-O-beta-D-glucopyranosyl-(1 --> 6)-beta-D-glucopyranosyl ester (6), 3-O-alpha-L-arabinopyranosyl-(1 --> 3)-[alpha-L-arabinopyranosyl-(1 --> 2)-]alpha-L-arabinopyranosyl-akebonic acid-28-O-beta-D-glucopyranosyl-(1 --> 6)-beta-D-glucopyranosyl ester (7).     

Triterpenoidal saponins from the barks of Zygophyllum fabago L

Two new triterpenoid saponins, zygophylosides O (1) and P (2), have been isolated from the barks of Zygophyllum fabago L. Their structures were elucidated as 3beta-[(2-O-sulfo-beta-D-xylopyranosyl)oxy]urs-12-ene-27,28-dioic acid and 3beta-[(2-O-sulfo-beta-D-xylopyranosyl)oxy]urs-12-ene-27,28-dioic acid 28-beta-D-glucopyranoside, respectively, by spectral and chemical evidence. Compound 1 showed weaker Nitric Oxide (NO) inhibitory activity.     

Four new steroid constituents from the waste residue of fibre separation from Agave americana leaves

Three new steroidal saponins, named agamenosides H-J (1-3), and a new cholestane steroid agavegenin D (4) were isolated from the waste residue of fibre separation from Agave americana leaves, together with six known steroids. Structures of the new compounds 1-4 were deduced to be (22S,23S,24R,25S)-24-[(beta-D-glucopyranosyl)oxy]-5alpha-spirostane-3beta,6alpha,23-triol 6-O-beta-D-glucopyranoside (1), (22S,23S,24R,25S)-5alpha-spirostane-3beta,23,24-triol 24-O-beta-D-glucopyranoside (2), (22S,23S,25R,26S)-23,26-epoxy-5alpha-furostane-3beta,22,26-triol 26-O-beta-D-glucopyranoside (3), and (22S,25S)-5alpha-cholestane-3beta,16beta,22,26-tetrol (4), respectively, by means of spectroscopic analysis, including extensive 1D and 2D NMR data, and the results of hydrolytic cleavage.     

Structural determination of three new eudesmanolides from Inula helenium

Ten sesquiterpenens were isolated from Inula helenium. Among them, three eudesmanolides: 15-hydroxy-11betaH-eudesm-4-en-8beta,12-olide (1), 3alpha-hydroxy-11betaH-eudesm-5-en-8beta,12-olide (2) and 2beta, 11alpha-dihydroxy-eudesm-5-en-8beta,12-olide (3) are new compounds. Their chemical structures were determined by spectral methods including 2D NMR.     

Five new nortropane alkaloids and six new amino acids from the fruit of Morus alba LINNE growing in Turkey

Investigation of the constituents of the fruits of Morus alba LINNE (Moraceae) afforded five new nortropane alkaloids (1-5) along with nor-psi-tropine (6) and six new amino acids, morusimic acids A-F (7-12). The structures of the new compounds were determined to be 2alpha,3beta-dihydroxynortropane (1), 2beta,3beta-dihydroxynortropane (2), 2alpha,3beta,6exo-trihydroxynortropane (3), 2alpha,3beta,4alpha-rihydroxynortropane (4), 3beta,6exo-dihydroxynortropane (5), (3R)-3-hydroxy-12-[(1S,4S)-4-[(1S)-1-hydroxyethyl]-pyrrolidin-1-yll-dodecanoic acid-3-O-beta-D-glucopyranoside (7), (3R)-3-hydroxy-12-[(1S,4S)-4-[(1S)-1-hydroxyethyl]-pyrrolidin-1-yll-dodecanoic acid (8), (3R)-3-hydroxy-12-1(1R,4R,5S)-4-hydroxy-5-methyl-piperidin-1-yll-dodecanoic acid-3-O-beta-D-glucopyranoside (9), (3R)-3-hydroxy-12-[(1R,4R,5S)-4-hydroxy-5-methyl-piperidin-1-yll-dodecanoic acid (10), (3R)-3-hydroxy-12-[(1R,4R,5S)-4-hydroxy-5-hydroxymethyl-piperidin-1-yl]-dodecanoic acid-3-O-beta-D-glucopyranoside (11), and (3R)-3-hydroxy-12-[(1R,4S,5S)-4-hydroxy-5-methyl-piperidin-1-yl]-dodecanoic acid (12) on the basis of spectral and chemical data.     

Triterpenes and saponins from Ilex psammophila

Two new saponins were isolated from the leaves of Ilex psammophila. Their structure was established by chemical and spectroscopic methods as 28-O-beta-D-glucopyranosylester of 20(S)-ilexgenin A ([structure: see text]) and 28-O-beta-D-glucopyranosylester of 20(S)-3beta,19alpha,24-trihydroxyurs-12-ene-23, 28-dioic acid ([structure: see text]).     

Sulfated lupane triterpene derivatives and a flavone C-glycoside from Gypsophila repens

A new sulfated lupane triterpene, Gypsophilin (1), and its glucosyl ester, Gypsophilinoside (2) were isolated from the roots of Gypsophila repens whereas a new flavone C-glycoside (3) was obtained from the aerial parts. Their structures were established as (3beta)-3-O-(sulfo)lup-20(29)-en-23,28-dioic acid (1), (3beta)-3-O-(sulfo)lup-20(29)-en-23,28-dioic acid -28-O-beta-D-glucopyranosyl ester (2) and luteolin-7-O-alpha-L-arabinopyranosyl-6-C-beta-glucopyranoside (3) by spectroscopic methods such as 1D and 2D NMR, HR-ESI-MS and FAB-MS.     

Two new bioactive oleanane triterpene glycosides from Terminalia arjuna

Two new oleanane-type triterpene glycosides designated as Termiarjunoside I and Termiarjunoside II were isolated from stem bark of Terminalia arjuna (Combretaceae) and characterized as olean-1alpha,3beta,9alpha,22alpha-tetraol-12-en-28-oic acid-3beta-D-glucopyranoside (1) and olean-3alpha,5alpha,25-triol-12-en-23,28-dioic acid-3alpha-D-glucopyranoside (2) based on chemical and spectral data evidences. Both compounds 1 and 2 potently suppressed the release of nitric oxide and superoxide from macrophages and also inhibited aggregation of platelets.     

A new unusual delta11(12)-oleane triterpene and anti-complementary triterpenes from Prunella vulgaris spikes

Anti-complementary activity-guided fractionation of the ethanolic extract of Prunella vulgaris spikes led to the isolation of a new, unusual delta11(12) triterpene, 3beta,13beta-dihydroxyolic-11-ene-28-oic acid (1), along with thirteen known triterpenes (2-14). The structure of the new compound was established by 1D and 2D NMR spectroscopic analysis. All the isolates were evaluated for their anti-complementary activity against the classical pathway (CP) and alternative pathway (AP). Eight triterpenes (1-8) showed anti-complementary activity against CP and AP, with CH50 and AP50 values of 0.15-0.37 mg/mL, and 0.29-0.53 mg/mL, respectively. Mechanism study using complement-depleted sera showed that oleanolic acid (2) acted selectively on C1q, C5, and C9 components, while 2alpha-hydroxy oleanolic acid (3) interacted with C1q, C3, C5 and C9, and 2alpha,3alpha-dihydroxyolic-12-ene-28-oic acid (4) blocked C1q, C2, C3, C5 and C9.