Phytochemistry (v.66, #23)

Unusually sulfated and oxygenated steroids from Withania somnifera by Laxminarain Misra; Payare Lal; Rajender S. Sangwan; Neelam S. Sangwan; Girish C. Uniyal; Rakesh Tuli (2702-2707).
Ten withasteroids have been isolated from Withania somnifera leaves, out of which four are new including a 3-sulfated steroid. Their structures have been established by spectroscopic methods.Four (1, 810) and six known (27) withanolides were isolated from the leaves of Withania somnifera. Among the new compounds, 10 possessed the rare 3-O-sulfate group with the saturation in A ring and 9 contained unusual 1,4-dien-3-one group. Compound 8 did not have usual 2,3 unsaturation in A ring while 1 had the rare C-16 double bond. The structures of all the compounds were elucidated by spectroscopic methods and chemical transformation.
Keywords: Withania somnifera L.; Solanaceae; Ashwagandha; Withanolides; Withasteroids; Sulfated; Oxygenated withanolide;

Three sesquiterpene hydrocarbons from the roots of Panax ginseng C.A. Meyer (Araliaceae) by Rita Richter; Simla Basar; Angelika Koch; Wilfried A. König (2708-2713).
Three sesquiterpene hydrocarbons (panaxene, panaginsene, and ginsinsene) have been isolated from roots of Panax ginseng. Structure elucidation resulted from spectroscopic methods (GC–MS, NMR).The volatile constituents of the roots of Panax ginseng C.A. Meyer have been investigated after hydrodistillation and analysed by means of different analytical methods. Besides several compounds already known three sesquiterpene hydrocarbons have been isolated from the essential oil. Structure elucidation of the bicyclic panaxene as well as of the tricyclic panaginsene and ginsinsene was performed by MS and NMR. They have been identified as (1R*,2S*,5S*)-2-ethenyl-1(1-methylethenyl)-2,6,6-trimethylbicyclo[3.2.0]heptane (panaxene), (1S*,8S*,11R*)-4,7,7,11-tetramethyltricyclo[6.3.0.01,5]undec-4-ene (panaginsene) und (1R*,6R*,7R*)-3,7,10,10-tetramethyltricyclo[4.3.2.02,6]undec-2-ene (ginsinsene).
Keywords: Panax ginseng; Araliaceae; Essential oil; Sesquiterpenes; Panaxene; Panaginsene; Ginsinsene;

Acylated farnesyl diglycosides from Guioa crenulata by Abdulmagid Alabdul Magid; Laurence Voutquenne-Nazabadioko; Marc Litaudon; Catherine Lavaud (2714-2718).
Chemical investigation of the methanolic extract of the leaves of Guioa crenulata led to the isolation and characterisation of four farnesyl diglycosides, crenulatosides A, B, C and D, along with three known flavonol glycosides and one known trimeric proanthocyanidin possessing a doubly linked structure.Chemical investigation of the methanol extract of the leaves of Caledonian Guioa crenulata led to the isolation and characterisation of four farnesyl diglycosides, crenulatosides A, B, C and D, along with three known flavonol glycosides and one known trimeric proanthocyanidin possessing a doubly linked structure. The structures of these compounds were determined on the basis of spectroscopic studies and chemical evidence. The ethanol and ethyl acetate extracts of the leaves exhibited no cytotoxic activity and no inhibition of acetylcholinesterase.
Keywords: Guioa crenulata; Sapindaceae; Farnesyl glycoside; Sesquiterpene; Kaempferol; Quercetin; Proanthocyanidin trimers;

Triterpenoid glycosides from Bacopa monnieri by Chillara Sivaramakrishna; Chirravuri V. Rao; Golakoti Trimurtulu; Mulabagal Vanisree; Gottumukkala V. Subbaraju (2719-2728).
Two triterpenoid saponins 1 and 2 were isolated from Bacopa monnieri along with 10 known compounds and their structures were elucidated on the basis of spectral data.Two triterpenoid glycosides have been isolated along with 10 known saponins from Bacopa monnieri. Structures of the compounds have been elucidated as 3-O-[β-d-glucopyranosyl-(1 → 3)-β-d-glucopyranosyl] jujubogenin (1) and 3-O-[β-d-glucopyranosyl-(1 → 3)-β-d-glucopyranosyl] pseudojujubogenin (2) by high resolution NMR spectral data and chemical correlations. Further, the chemical compositions of bacosides A and B have been delineated.
Keywords: Bacopa monnieri; Scrophulariaceae; Bacoside A; Bacoside B; Jujubogenin; Pseudojujubogenin; Triterpenoid saponin;

Unusual cyclolanostanes from leaves of Pandanus boninensis by Akira Inada; Yasuyuki Ikeda; Hiroko Murata; Yuka Inatomi; Tsutomu Nakanishi; Kinkini Bhattacharyya; Tanusree Kar; Gabriele Bocelli; Andrea Cantoni (2729-2733).
Two unusual triterpenoids, (24S)-24-methyl-25,32-cyclo-5α-lanosta-9(11)-en-3β-ol and (24S)-24-methyl-25,32-cyclo-cycloartane-3β-ol, were isolated from leaves of Pandanus boninensis. Their structures were established on the basis of spectroscopic methods and X-ray analysis.Two unusual triterpenoids, (24S)-24-methyl-25,32-cyclo-5α-lanosta-9(11)-en-3β-ol and (24S)-24-methyl-25,32-cyclo-cycloartane-3β-ol, were isolated from leaves of Pandanus boninensis along with known triterpenoids and lignans. Their structures were established on the basis of spectroscopic methods and X-ray analysis.
Keywords: Pandanus boninensis; Pandanaceae; Leaf; Triterpenoid; 25,32-Cyclolanostane; Lignan;

Quassinoids from the leaves of the Madagascan Simaroubaceae Samadera madagascariensis by Philip H. Coombes; Dashnie Naidoo; Dulcie A. Mulholland; Milijaona Randrianarivelojosia (2734-2739).
The leaves of Samadera madagascariensis have yielded three C18 quassinoids, 5β,6-dihydrosamaderine A, 2-chlorosamaderine A, and samaderolactone A, and a C19 quassinoid, 3,4β-dihydrosamaderine C, together with the known quassinoids samaderine A, samaderine B, and cedronin.An investigation of the leaves of the Madagascan Simaroubaceae Samadera madagascariensis has yielded three C18 quassinoids, 5β,6-dihydrosamaderine A, 2-chlorosamaderine A, and samaderolactone A, and a C19 quassinoid, 3,4β-dihydrosamaderine C, together with the known quassinoids samaderine A, samaderine B, and cedronin. The compounds isolated displayed little or no anti-tumour activity.
Keywords: Samadera madagascariensis; Simaroubaceae; Madagascar; Quassinoids; Samaderine A; Samaderolactone A; 2-Chlorosamaderine A; 5β,6-Dihydrosamaderine A; Samaderine B; 3,4β-Dihydrosamaderine C; Cedronin; Anti-tumour activity;

Biflavonoids from Lonicera japonica by Neeraj Kumar; Bikram Singh; Pamita Bhandari; Ajai P. Gupta; Sanjay K. Uniyal; Vijay K. Kaul (2740-2744).
Two biflavonoids, 3′-O-methyl loniflavone [5,5″,7,7″-tetrahydroxy 3′-methoxy 4′,4‴-biflavonyl ether] and loniflavone [5,5″,7,7″,3′-pentahydroxy 4′,4‴-biflavonyl ether] along with luteolin and chrysin were isolated and characterized from the leaves of Lonicera japonica.Two biflavonoids, 3′-O-methyl loniflavone [5,5″,7,7″-tetrahydroxy 3′-methoxy 4′,4‴-biflavonyl ether (1)] and loniflavone [5,5″,7,7″,3′-pentahydroxy 4′,4‴-biflavonyl ether (2)] along with luteolin (3) and chrysin (4) were isolated from the leaves of Lonicera japonica. The structures were established on the basis of UV/vis, 1D, 2D NMR (HMQC and HMBC) and ESI-QTOF-MS/MS spectroscopic methods and chemical evidences.
Keywords: Lonicera japonica; Caprifoliaceae; Biflavone; 3′-O-methyl loniflavone; Loniflavone;

Bioactive constituents from roots of Bursera tonkinensis by Aranya Jutiviboonsuk; Hongjie Zhang; Ghee Teng Tan; Cuiying Ma; Nguyen Van Hung; Nguyen Manh Cuong; Nuntavan Bunyapraphatsara; D. Doel Soejarto; Harry H.S. Fong (2745-2751).
Bioassay directed-fractionation led to the isolation of 12 compounds, including the lignan (A), the phenylpropane derivative (B), and the neolignan (C) from the roots of Bursera tonkinensis Guillaum (Burseraceae). The structures were determined by spectroscopic methods. Of these only 4′-demethyldesoxypodophyllotoxin exhibited significant cytotoxic activities against KB, Col2 and LNCaP cell lines.Bioassay directed-fractionation led to isolation of 12 compounds from the roots of Bursera tonkinensis Guillaum (Burseraceae), including burselignan, bursephenylpropane, and burseneolignan. Of the 12 compounds, only 4′-demethyldesoxypodophyllotoxin exhibited significant cytotoxic activities against KB, Col2 and LNCaP cell lines.
Keywords: Bursera tonkinensis; Burseraceae; Cytotoxicity; Burselignan; Burseneolignan; Bursephenylpropane;

Four phenolic glycosides, cuneatasides A–D, and one ionone glycoside cuneataside E were isolated from the water-soluble constituents of the stem of Sargentodoxa cuneata. Of these, in vitro tests for antimicrobial activity showed compounds 1 and 2 to possess significant activity against two Gram-positive organisms, Staphylococcus aureus and Micrococcus epidermidis.Four phenolic glycosides, cuneatasides A–D (14), and one ionone glycoside cuneataside E (5), together with seven known phenolic compounds (612) were isolated from the water-soluble constituents of the stem of Sargentodoxa cuneata (Sargentodoxaceae). Their structures were elucidated by spectroscopic analysis. In vitro tests for antimicrobial activity showed compounds 1 and 2 to possess significant activity against two Gram-positive organisms, Staphylococcus aureus and Micrococcus epidermidis.
Keywords: Sargentodoxa cuneata; Sargentodoxaceae; Phenolic glycosides; Ionone glycoside; Cuneatasides A–E; Antimicrobial activity;

Four flavonoids with 2′,4′-di-oxygenated B-rings were isolated from an ethanolic extract of the roots of Cudrania cochinchinensis, including an unusual flavonoid-Mg2+ salt. Their structures were elucidated by chemical and spectroscopic methods. Cytotoxic activities were evaluated against several different cell lines.Four flavonoids with 2′,4′-di-oxygenated B-rings, cochinchinol A (1), cochinchinol B (2), (2R,3R)-4′,7-dihydroxy-2′,5-dimethoxydihydroflavonol (3), 4′,7-dihydroxy-2′,5-dimethoxyflavonol (4), along with 11 known compounds, were isolated from an ethanolic extract of the roots of Cudrania cochinchinensis. Their structures were elucidated by chemical and spectroscopic methods. Cochinchinol A (1) and cochinchinol B (2) have two hitherto unprecedented flavonol salt structures in natural product chemistry. Cytotoxic activities were evaluated against several different cell lines.
Keywords: Cudrania cochinchinensis; Moraceae; Flavonoids; Flavonol salt; Cochinchinol A; Cochinchinol B; (2R,3R)-4′,7-dihydroxy-2′,5-dimethoxydihydroflavonol; 4′,7-dihydroxy-2′,5-dimethoxy flavonol;

Negative ion electrospray mass spectrometry of neoflavonoids by Alison N. Hulme; Hamish McNab; David A. Peggie; Anita Quye (2766-2770).
Negative ion electrospray ionisation (ESI) mass spectra of the neoflavonoids brazilin and hematoxylin under collision induced decomposition (CID) conditions show fragments characteristic of rings A and C. In their oxidised forms, the fragments are characteristic of rings B and D.The electrospray ionisation mass spectra of the neoflavanoids brazilin and hematoxylin are reported in both their reduced (1 and 2, respectively) and their oxidised forms (3 and 4, respectively). In the reduced forms, breakdown pathways under collision induced decomposition (CID) conditions produce fragments characteristic of rings A and C; in their oxidised forms, the fragments are characteristic of rings B and D. The structural assignments of the fragments are substantiated by recording the spectra after deuterium exchange at the hydroxyl groups.
Keywords: Neoflavonoids; Mass spectrometry;

Phomoxins B and C: Polyketides from an endophytic fungus of the genus Eupenicillium by Rohan A. Davis; Vesna Andjic; Michael Kotiw; Roger G. Shivas (2771-2775).
Chemical investigations of the culture broth from an endophytic fungus Eupenicillium sp. have afforded two new natural products phomoxins B (1) and C (2) as well as the previously reported fungal metabolite eupenoxide.Chemical investigations of the culture broth from an endophytic fungus Eupenicillium sp. have afforded two natural products phomoxins B (1) and C (2) as well as the previously reported fungal metabolite eupenoxide (3). Compounds 1 and 2 both contain a cyclic carbonate moiety that is rare among natural products. This paper reports the full spectroscopic characterisation of phomoxins B (1) and C (2) by NMR, UV, IR and MS data. All compounds were inactive against a panel of nosocomial microbes.
Keywords: Endophytic fungus; Eupenicillium sp.; Glochidion ferdinandi; Natural products; Polyketides; Phomoxin B; Phomoxin C; Eupenoxide; Cyclic carbonate;

4-Benzyl-3-phenyl-5H-furan-2-one, a vasodilator isolated from Malbranchea filamentosa IFM 41300 by Tomoo Hosoe; Toru Iizuka; Shin-ichirou Komai; Daigo Wakana; Takeshi Itabashi; Koohei Nozawa; Kazutaka Fukushima; Ken-ichi Kawai (2776-2779).
Screening of Malbranchea filamentosa IFM 41300 for bioactive compounds led to the discovery of the furanone derivative (1) as a vasodilator and the isolation of erythroglaucin (2). The structure of 1 was established on the basis of spectroscopic and chemical investigations.Screening of Malbranchea filamentosa IFM 41300 for bioactive compounds led to the identification of 4-benzyl-3-phenyl-5H-furan-2-one (1) as a vasodilator and erythroglaucin (2). The structure of 1 was established on the basis of spectroscopic and chemical investigations. Compound 1 inhibited Ca2+-induced vasocintraction in aortic rings pretreated with high K+ (60 mM) or norepinephrine. Finally, compound 1 did not exhibit activity against human pathogenic microorganisms.
Keywords: 4-Benzyl-3-phenyl-5H-furan-2-one; Vasodilator; Malbranchea filamentosa fungus; Chemical structure;

Phytochemical constituents and hepatoprotective activity of Viburnum tinus by Mona A. Mohamed; Mohamed S.A. Marzouk; Fatma A. Moharram; Mortada M. El-Sayed; Ayman R. Baiuomy (2780-2786).
From the Leaves of Viburnum tinus L. four metabolites viz viburtinoside A and B (acylated iridoid glucosides), scopoletin 7-O-β-d-sophoroside and natural occurred 2,6-di-C-methyl-nicotinic acid 3,5-diethyl ester with 10 known metabolites were isolated. Toxicity and CCl4-induced hepatotoxicity of the investigated extract have been evaluated in terms of the determination of ALT, AST, lipid peroxide and nitric oxide levels in serum.From the leaves of Viburnum tinus L. (Adoxaceae) two acylated iridoid glucosides (viburtinoside A and B), a coumarin diglucoside scopoletin 7-O-β-d-sophoroside and a natural occurred dinicotinic acid ester 2,6-di-C-methyl-nicotinic acid 3,5-diethyl ester were isolated. In addition to these, 10 known compounds were isolated, namely two bidesmosidic saponins, a hexamethoxy-flavone and five flavonol glycosides, as well as suspensolide A and oleanolic acid were isolated for the first time in this genus and species, respectively. The structures were determined mainly by spectroscopic methods (UV, IR, ESI-MS, 1H-, 13C NMR and DEPT). Toxicity of the investigated extract was determined (LD50  = 500 mg/kg). CCl4-induced hepatotoxicity has been evaluated in terms of the determination of alanine aminotransferase (ALT), aspartate aminotransferase (AST), lipid peroxide and nitric oxide levels in serum and compared using adult male rats weighing 150–180 g. Their highly elevated levels were significantly reduced by treatment with the investigated aqueous methanol extract in dose-dependant manner.
Keywords: Viburnum tinus; Adoxaceae; Acylated iridoid glucosides; Nicotinic acid diethyl ester; Coumarin sophoroside; Hepatoprotective activity; Lipid peroxidation; Nitric oxide;

Halogenated metabolites from Japanese Laurencia spp. by Minoru Suzuki; Tomotake Kawamoto; Charles Santhanaraju Vairappan; Takahiro Ishii; Tsuyoshi Abe; Michio Masuda (2787-2793).
Two halogenated metabolites, a labdane-type diterpene and a C15 acetogenin possessing a terminal bromoallene group, were isolated from Japanese Laurencia spp. and identified by spectroscopic analysis.Further investigation of Laurencia species from Japanese waters, which were collected at three locations, yielded brominated metabolites, a labdane- type diterpene and a C15 acetogenin possessing a terminal bromoallene group. Their structures were deduced from analysis of spectroscopic data.
Keywords: Laurencia; Rhodomelaceae; Red alga; C15 acetogenin; Diterpene; Sesquiterpene; Halogenated compound; Chemotaxonomy;

Author Index (2796).