Structural determination of two new steroidal saponins from Smilax china

Two new steroidal saponins (1 and 2) were isolated from the BuOH fraction of the 70% EtOH extract of the tubes of Smilax china, together with four known analogues, 3–6. The structures of the new compounds were elucidated by means of chemical evidence and spectroscopic analyses, including HR‐MS, IR, ¹H‐ and ¹³C‐NMR, and 2D experiments (¹H–¹H COSY, HSQC and HMBC). Copyright © 2009 John Wiley & Sons, Ltd.     

Structural determination of flavonoids from Sophora flavescens

Eight flavonoids were isolated from Sophora flavescens. Among them, three prenylflavanones: (2S)-6[2(3-hydroxyisopropyl)-5-methyl-4-hexenyl]-5-methoxy-7,2', 4'-trihydroxyflavanone (1), (2S)-5, 4'-dimethoxy-8-lavandulyl-7, 2'-dihydroxy flavanone (2) and (2S)-8-(5-hydroxy-2-isopropenyl-5-methylhexyl)-7-methoxy-5,2', 4'-trihydroxyflavanone (3) are new compounds. Their chemical structures were determined by spectral methods including 2D NMR.     

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.     

Complete 1H and 13C NMR assignments for two new monodesmoside saponins from Pentaclethra macroloba (Willd.) Kuntze

A detailed NMR study and full assignments of the 1H and 13C spectral data for two novel triterpenoid saponins isolated from the stem bark of Pentaclethra macroloba (Willd.) Kuntze are described. Their structures were established using a combination of 1D and 2D NMR techniques including 1H,1H-COSY, TOCSY, NOESY, gs-HMQC and gs-HMBC, and also electrospray ionization mass spectrometry and chemical methods. The structures were established as 3beta-O-([O-beta-D-glucopyranosyl-(1-->2)-O-beta-D-glucopyranosyl-(1-->4)-O-beta-D-glucopyranosyl-(1-->3)-O-alpha-L-rhamnopyranosyl-(1-->2)]-[O-beta-D-glucopyranosyl-(1-->3)-O-beta-D-glucopyranosyl-(1-->4)])-alpha-L-arabinopyranosylhederagenin (1) and 3beta-O-)[O-beta-D-glucopyranosyl-(1-->2)-O-beta-D-glucopyranosyl-(1-->4)-O-beta-D-glucopyranosyl-(1-->3)-O-alpha-L-rhamnopyranosyl-(1-->2)]-[O-beta-D-glucopyranosyl-(1-->3)-O-beta-D-glucopyranosyl-(1-->4)])-alpha-L-arabinopyranosyloleanolic acid (2).     

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).     

Complete assignments of 1H and 13C NMR spectroscopic data for two new triterpenoid saponins from Ilex hainanensis

Two novel unsaturated E-ring pentacyclic triterpenoid saponins, ilexhainanoside A and ilexhainanoside B, were isolated from the leaves of Ilex hainanensis. Their chemical structures were determined by MS, NMR spectroscopy and chemical analysis. Complete assignments of the 1H and 13C NMR spectroscopic data were achieved by 1D and 2D NMR experiments (HSQC, HMBC, ROESY and 1H-1H COSY).     

1H and 13C NMR spectral data of new saponins from Cordia piauhiensis

Two new bidesmoside triterpenoid saponins were isolated from stems of Cordia piauhiensis. Their structures, characterized as 3-O-alpha-L-rhamnopyranosyl-(1 --> 2)-beta-D-glucopyranosyl pomolic acid 28-O-beta-D-glucopyranosyl ester (1) and 3-O-alpha-L-rhamnopyranosyl-(1 --> 2)-beta-D-glucopyranosyl oleanolic acid 28-O-beta-D-glucopyranosyl-(1 --> 6)-beta-D-glucopyranosyl ester (2), were unequivocally established after extensive NMR (1H, 13C, DEPT 135 degrees, COSY, HSQC, HMBC, TOCSY, and NOESY) studies.     

Two new complex triterpenoid saponins from Gledistsia dolavayi Franch.

Two new triterpenoid saponins, gledistside A ( 1 ) and gledistside B ( 2 ), isolated from the fruits of Gledistsia dolavayi Franch., were characterized as the 3,28‐O‐bisdesmoside of echinocystic acid acylated with monoterpene carboxylic acids. On the basis of spectroscopic and chemical evidence, their structures were elucidated as 3‐O‐β‐D ‐xylopyranosyl‐(1→2)‐α‐L ‐arabinopyranosyl‐(1→6)‐β‐D ‐glucopyranosyl‐28‐O‐β‐D ‐xylopyranosyl‐(1→3)‐β‐D ‐xylopyranosyl‐(1→4)‐[β‐D ‐galactopyranosyl‐(1→2)]‐α‐L ‐rhamnopyranosyl‐(1→2)‐{6‐O‐[2,6‐dimethyl‐6(S)‐hydroxy‐2‐trans‐2,7‐octadienoyl]}‐β‐D ‐glucopyranosylechinocystic acid ( 1 ) and 3‐O‐β‐D ‐xylopyranosyl‐(1→2)‐α‐L ‐arabinopyranosyl‐(1→6)‐β‐D ‐glucopyranosyl‐28‐O‐β‐D ‐xylopyranosyl‐(1→3)‐β‐D ‐xylopyranosyl‐(1→4)‐[β‐D ‐galactopyranosyl‐(1→2)]‐α‐L ‐rhamnopyranosyl‐(1→2)‐{6‐O‐[2‐hydroxymethyl‐6‐methyl‐6(S)‐hydroxy‐2‐trans‐2,7‐octadienoyl]}‐β‐D ‐glucopyranosylechinocystic acid ( 2 ). The complete ¹H and ¹³C assignments of saponins 1 and 2 were achieved on the basis of 2D NMR spectra including HMQC‐TOCSY, TOCSY, ¹H–¹H COSY, HMBC, ROESY and HMQC spectra. Copyright © 2002 John Wiley & Sons, Ltd.     

Structural elucidation and NMR spectral assignment of three new furostanol saponins from the roots of Tupistra chinensis

Three new furostanol saponins (1–3) were isolated from the roots of Tupistra chinensis (T. chinensis). And their structures were elucidated on the basis of NMR and mass spectrometry (MS) spectral analysis. Copyright © 2009 John Wiley & Sons, Ltd.     

New saponins from Sechium mexicanum

The chemical study of Sechium mexicanum roots led to the isolation of the two new saponins {3‐O‐β‐D ‐glucopyranosyl (1 → 3)‐β‐D ‐glucopyranosyl‐2β,3β,16α,23‐tetrahydroxyolean‐12‐en‐28‐oic acid 28‐O‐α‐L ‐rhamnopyranosyl‐(1 → 3)‐β‐D ‐xylopyranosyl‐(1 → 4)‐α‐L ‐rhamnopyranosyl‐(1 → 2)‐α‐L ‐arabinopyranoside} (1) and {3‐O‐β‐D ‐glucopyranosyl (1 → 3)‐β‐D ‐glucopyranosyl‐2β,3β,16α,23‐tetrahydroxyolean‐12‐en‐28‐oic acid 28‐O‐α‐L ‐rhamnopyranosyl‐(1 → 3)‐β‐D ‐xylopyranosyl‐(1 → 4)‐[β‐D ‐apiosyl‐(1 → 3)]‐α‐L ‐rhamnopyranosyl‐(1 → 2)‐α‐L ‐arabinopyranoside} (2), together with the known compounds {3‐O‐β‐D ‐glucopyranosyl‐(1 → 3)‐β‐D ‐glucopyranosyl‐2β,3β,6β,16α,23‐pentahydroxyolean‐12‐en‐28‐oic acid 28‐O‐α‐L ‐rhamnopyranosyl‐(1 → 3)‐β‐D ‐xylopyranosyl‐(1 → 4)‐α‐L ‐rhamnopyranosyl‐(1 → 2)‐α‐L ‐arabinopyranoside} (3), tacacosides A₁ (4) and B₃ (5). The structures of saponins 1 and 2 were elucidated using a combination of ¹H and ¹³C 1D‐NMR, COSY, TOCSY, gHMBC and gHSQC 2D‐NMR, and FABMS of the natural compounds and their peracetylated derivates, as well as by chemical degradation. Compounds 1–3 are the first examples of saponins containing polygalacic and 16‐hydroxyprotobasic acids found in the genus Sechium, while 4 and 5, which had been characterized partially by NMR, are now characterized in detail. Copyright © 2009 John Wiley & Sons, Ltd.     

Two new triterpenoid saponins from Pittosporum senacia Putterlick (Pittosporaceae)

From the branches of Pittosporum senacia Putterlick (Pittosporaceae), two new triterpenoid saponins, senaciapittosides A and B (1, 2), were isolated. Their structures were elucidated by extensive analysis of one‐ and two‐dimensional nuclear magnetic resonance spectroscopy, high‐resolution electrospray ionization mass spectrometry (HR‐ESIMS) and chemical evidence as 3‐O‐[β‐d ‐glucopyranosyl‐(1 → 2)]‐[α‐l ‐arabinopyranosyl‐(1 → 3)]‐[α‐l ‐arabinofuranosyl‐(1 → 4)]‐β‐d ‐glucuronopyranosyl oleanolic acid 28‐O‐β‐d ‐glucopyranosyl ester (1) and 3‐O‐[β‐d ‐glucopyranosyl‐(1 → 2)]‐[α‐l ‐arabinopyranosyl‐(1 → 3)]‐[α‐l ‐arabinofuranosyl‐(1 → 4)]‐β‐d ‐glucuronopyranosyl‐22‐O‐α‐l ‐arabinopyranosyl‐21‐acetoxy R1‐barrigenol (2). Compound 2 presents an unusual glycosylation at C‐22 of its aglycone. Copyright © 2012 John Wiley & Sons, Ltd.     

Structure elucidation and complete NMR spectral assignments of two new oleanane‐type pentacyclic triterpenoid saponins from the husks of Xanthoceras sorbifolia Bunge

Two new saponins were isolated from husks of Xanthoceras sorbifolia Bunge and their structures were elucidated as 3‐O‐[β‐D‐galactopyranosyl(1→2)]‐α‐L‐arabinofuranosyl(1→3)‐β‐D‐methyl glucuronic acid‐21‐O‐(3,4‐diangeloyl)‐α‐L‐rhamnose‐3β, 16α, 21β, 22α, 28β‐pentahydroxyl‐22‐acetoxy‐olean‐12‐ene(1) and 3‐O‐[β‐D‐galactopyranosyl(1→2)]‐α‐L‐arabinofuranosyl(1→3)‐β‐D‐methyl glucuronic acid‐21,22‐O‐diangeloyl‐3β,15α,16α,21β,22α,28β‐hexahydroxyl‐olean‐12‐ene(2) on the basis of 1D and 2D NMR (including ¹H, ¹³C‐NMR, ¹H? ¹H COSY, HSQC, HMBC and DEPT), ESI‐MS spectrometry and chemical methods. Copyright © 2009 John Wiley & Sons, Ltd.     

Tupisteroide A–C,three new polyhydroxylated steroidal constituents from the roots of Tupistra chinensis

Three new steroidal compounds with polyhydroxy groups, tupisteroide A–C (1–3), were obtained from the roots of Tupistra chinensis, together with one known compound (4) that was isolated from this plant for the first time. The structures of tupisteroide A–C were determined on the basis of one‐ and two‐dimensional NMR spectroscopy, including ¹H–¹H Correlation Spectroscopy, Heteronuclear Multiple Bond Correlation, and Heteronuclear Single Quantum Coherence experiments. The isolated compounds were evaluated for their cytotoxic activities against A549, HepG2, and CaSki cancer cell lines in vitro. Among them, compounds 1, 2, and 4 did not show significant inhibitory activity, but compound 3 showed cytotoxicity against A549 cancer cell lines with IC₅₀ values of 25.0 μM. Copyright © 2012 John Wiley & Sons, Ltd.     

Structural and spectral assignment of three forskolin-like diterpenoids isolated from Plectranthus ornatus

Three labdane diterpenoids were isolated from an acetone extract of Plectranthus ornatus. Their structures, closely related to that of forskolin, were determined by NMR studies. Unambiguous and complete assignments of the 1H and 13C NMR chemical shifts for these substances are presented. The assignments are based on 2D shift-correlated [1H, 1H-COSY, 1H, 13C-gHSQC-1J (C,H), 1H, 13C-gHMBC-(n)J (C,H) (n = 2 and 3)] and NOE experiments.     

Structural determination of two new triterpenoids biotransformed from glycyrrhetinic acid by Mucor polymorphosporus

Five hydroxylated derivatives of glycyrrhetinic acid by Mucor polymorphosporus were isolated. Among them, 6β, 7β‐dihydroxyglycyrrhentic acid (2) and 27‐hydroxyglycyrrhentic acid (3) are new compounds. Their chemical structures were identified by spectral methods including 2D‐NMR. Copyright © 2009 John Wiley & Sons, Ltd.     

Complete assignments of 1H and 13C NMR spectra of leucanthoside A, a new triterpenoid saponin from Cephalaria leucantha L

Leucanthoside A, a new allose-containing triterpenoid saponin (1), was isolated from the aerial parts of Cephalaria leucantha L. Its structure was determined by electrospray ionization mass spectrometry and NMR spectroscopy. Complete assignments of the 1H and 13C NMR chemical shifts were achieved by two-dimensional NMR experiments: DQF-COSY, NOESY, TOCSY, HSQC, DINE-HSQC, HMBC, 13C-1H 2D-J-resolved spectroscopy, and 1,1-ADEQUATE.     

Structure elucidation and complete NMR spectral assignments of glucosylated saponins of cantalasaponin I

Five new glucosylated steroidal glycosides, cantalasaponin I‐B₁ (1), I‐B₂ (2), I‐B₃ (3), I‐B₄ (4) and I‐B₅ (5), were isolated and purified from the transformed product of the cantalasaponin I by using Toruzyme 3.0 l as biocatalyst. Their structures were elucidated on the basis of high‐resolution electrospray ionization mass spectrometry, one‐dimensional (¹H and ¹³C NMR) and two‐dimensional [COSY, heteronuclear single‐quantum correlation (HSQC), HMBC and HSQC‐TOCSY] NMR spectral analyses and chemical evidence. Copyright © 2012 John Wiley & Sons, Ltd.     

Structure determination of selaginellins G and H from Selaginella pulvinata by NMR spectroscopy

Selaginellins G ( 1 ) and H ( 2 ), two new selaginellin derivatives, were isolated from the whole plant of Selaginella pulvinata. Their structures were elucidated, and complete assignments of the ¹H and ¹³C NMR spectroscopic data were achieved by 1D and 2D NMR experiments (HSQC, HMBC, COSY and ROESY). Compound 1 displayed good antifungal activity against Candida albicans with an IC₅₀ value of 5.3 µg/ml. Copyright © 2010 John Wiley & Sons, Ltd.     

1H and 13C NMR assignments for four triterpenoid saponins from Albizziae cortex

Four triterpenoid saponins were isolated from Albizziae cortex, and a complete assignment of their (1)H and (13)C NMR spectra was carried out using 1D and 2D NMR ((1)H-(1)H COSY, HSQC, HMBC, and HSQC-TOCSY) methods. Their (1)H NMR assignments were reported for the first time and some of their (13)C NMR spectral data reported in literature were corrected.     

Structural and spectral assignments of six anthraquinone derivatives from the mangrove fungus (ZSUH-36)

A new natural product named 6,8,1'-tri-O-methyl averantin (1) has been isolated together with five known anthraquinones 1'-O-methyl averantin (2), 6,8-di-O-methyl averufin (3) averufin (4), versicolorin C (5) and 6,8-di-O-methyl averufanin (6) from a mangrove endophytic fungus ZSUH-36 collected from the South China Sea. NMR techniques including COSY, HMQC, and HMBC were used to elucidate the structures of these compounds. We report the unambiguous assignments of the (1)H and (13)C NMR spectra of the new compound 6,8,1'-tri-O-methyl averantin(1).