Two new epoxysteroids from Helianthus tuberosus

Two new epoxy steroids, 5α,8α-epidioxy-22β,23β-epoxyergosta-6-en-3β-ol (1) and 5α,8α-epidioxy-22α,23α-epoxyergosta-6-en-3β-ol (2), and ten known steroids including (24R)-5α,8α-epidioxyergosta-6-en-3β-ol (3), (22E,24R)-5α,8α-epidioxyergosta-6,22-dien-3β-ol (4), (22E,24R)-5α,8α-epidioxyergosta-6,9(11),22-trien-3β-ol (5), β-sitosterol (6), sitost-5-en-3β-ol acetate (7), 7α-hydroxysitosterol (8), schleicheol 2 (9), (24R)-24-ethyl-5α-cholestane-3β,5α,6β-triol (10), 7α-hydroxystigmasterol (11), and stigmasterol (12) were isolated from Helianthus tuberosus grown in Laizhou salinized land of coastal zone of Bohai Sea, China. The structures of these compounds were unambiguously established by 1D, 2D NMR and mass spectroscopic techniques. The new compounds 1 and 2 exhibited weak antibacterial activity and no antifungal activity.     

Chemical constituents from Aphanamixis grandifolia

(23E)-25-Methylcycloart-23-en-3β-ol (1), a cycloartane-type triterpenoid featuring an unusual skeleton of 31 carbon atoms, (17E)-cycloart-17,26-dien-3β-ol (2), a new cycloartane-type triterpenoid, and the other two new compounds 4R-hydroxy-4-(9S-hydroxy-12-methylhexan-6-yl)-3-methylcyclopent-2-enone (6) and 7-hydroxy-5-(2'-hydroxy-4',5'-dimethoxyphenyl)-2-methoxy-6-methyl-1,4-naphthoquinone (7), together with three known cycloart-3β-ol triterpenoids (3-5) were isolated from aerial parts of Aphanamixis grandifolia. Their structures were elucidated by spectroscopic analysis, and that of 1 was confirmed by single-crystal X-ray diffraction. The absolute configuration of two carbon stereocenters of compound 6 was determined to be 4R,9S by means of circular dichroism (CD) and auxiliary chiral α-methoxy-α-(trifluoromethyl)phenylacetic acid (MTPA) derivatives, respectively. The compound 3 exhibited significant cytotoxicities against HL-60, Hep G2 and HeLa, and compounds 1, 2, 5, 6 and 7 exhibited modest cytotoxicities. No activity of compound 4 could be due to the absence of the hydroxyl group at C-24.     

Antibacterial sphingolipid and steroids from the black coral Antipathes dichotoma

From the black coral Antipathies dichotoma, a sphingolipid (2S*,3S*,4E,8E)-2N-[tetradecanoyl]-4(E),8(E)-icosadiene-1,3-diol (1) and a steroid (22E)-methylcholesta-5,22-diene-1α,3β,7α-triol (2) were isolated. Other known compounds, 3β,7α-dihydroxy-cholest-5-ene (3), (22E,24S),5α,8α-epidioxy-24-methylcholesta-6,22-dien-3β-ol (4) and (22E,24S),5α,8α-epidioxy-24-methylcholesta-6,9(11),22-trien-3β-ol (5). The structures were established on the basis of NMR spectroscopic analysis and comparison with literature. The antibacterial activity of five compounds was evaluated.     

Studies on the Constituents of Ganoderma Lucidum

The methanolic extract of fruit bodies of cultivated Ganoderma lucidum was separated by silica gel column chromatography and preparative thin-layer chromatography to give ten compounds. On the basis of spectral analysis, chemical procedures and gas chromatography, d-mannitol (1), ergosta-7, 22-dien-3β-yl palmitate (2), ergosterol (3), ergosta-7, 22-dien-3β-ol (4), 5α-lanosta-7,9(11),24-trien-3β,26-diol (5), ergosterol peroxide (6), 24,25,26-trihydroxy-5α-lanosta-7,9(11)-dien-3-one (7), 5α-lanosta-7,9(11)-dien-3β,24,25,26-tetraol (8) and 8,9-epoxyergosta-5,22-dien-3β,15-diol (9) were identified. Among these compounds, 8,9-epoxyergosta-5,22-dien-3β,15-diol was first separated from Ganoderma lucidum.     

Photosensitized Oxygenation of Abieta-7,9(11)-dien-13β-ol

Dehydration of abiet-8-ene-7β, 13β-diol (ibozol, 1 ) leads to abieta-7,9(11)-dien-13β-ol ( 2 ) which aromatizes slowly to the known abieta-8,11,13-triene ( 3 ). Photosensitized oxygenation of the heteroannular diene 2 yields a mixture from which three compounds were identified; abiet-7-ene-9α, 11α, 13β-triol ( 4 ), abieta-8,11,13-trien-7-one ( 5 ), and abieta-8,11,13-trien-7α-ol ( 6 ).     

Specific oxidation of C-14 oxygenated 4(20),11-taxadienes by microbial transformation

Three C-14 oxygenated taxanes, 2α,5α,10β,14β-tetraacetoxytaxa-4(20),11-diene (1), 2α,5α,10β-triacetoxy-14β-(2-methylbutyryloxy)taxa-4(20),11-diene (2), and yunanaxane (3), major products of callus cultures of Taxus spp., were regio- and stereoselectively hydroxylated at the 7β position by a fungus, Absidia coerulea IFO 4011. Intriguingly, when 1 was co-administered with β-cyclodextrin and incubated with the fungus cell cultures, three other compounds 5α,9α,10β,13α-tetraacetoxytaxa-4(20),11-dien-14β-ol (7), 5α,9α,10β,13α-tetraacetoxytaxa-4(20),11-dien-1β-ol (8) and 5α,9α,10β,13α-tetraacetoxy-11(15→1) abeotaxa-4(20),11-dien-15-ol (9) were obtained.     

Chemical Constituents of a Formosan Soft Coral Sinularia sp.

A new marine sterol 7β-hydroperoxy-24-methylenecholesterol ( 1 ) along with five known compounds sarcophytol A ( 2 ), (Z)-N-[2-(4-hydroxyphenyl)ethyl]-3-methyldodec-2-enamide ( 3 ), 5α,7αH-eduesm-11(13)en-4α-ol ( 4 ), 24-methylenecholesterol ( 5 ) and 1β-hydroxy-α-cyperone ( 6 ) have been isolated from a Formosan soft coral Sinularia sp. The structures of the above compounds were determined by spectral analyses. Cytotoxicity of compounds 1–6 toward various cancer cell lines also is reported.     

20, 21-Azirdin-Steroide: Reaktion von Derivaten der Oxime von 5-Pregnen-20-on,9β,10α-5-Pregnen-20-on und 9β,10α-5,7-Pregnadien-20-on mit Lithiumaluminiumhydrid und von 3β-Hydroxy-5-pregnen-20-on-oxim mit Grignard-Verbindungen

20, 21-Aziridine Steroids: Reaction of Derivatives of the Oximes of 5-Pregnen-20-one, 9β, 10α-5-Pregnen-20-one and 9β, 10α-5,7-Pregnadiene-20-one with Lithium Aluminium Hydride, and of 3β-Hydroxy-5-pregnen-20-one Oxime with Grignard Reagents. Reduction of 3β-hydroxy-5-pregnen-20-one oxime ( 2 ) with LiAlH₄ in tetrahydrofuran yielded 20α-amino-5-pregnen-3β-ol ( 1 ), 20β-amino-5-pregnen-3β-ol ( 3 ), 20β, 21-imino-5-pregnen-3β-ol ( 6 ) and 20β, 21-imino-5-pregnen-3β-ol ( 9 ). The aziridines 6 and 9 were separated via the acetyl derivatives 7 and 10 . The reaction of 6 and 9 with CS₂ gave 5-(3β-hydroxy-5-androsten-17β-yl)-thiazolidine-2-thione ( 8 ). Treatment of the 20-oximes 12 and 15 of the corresponding 9β,10α(retro)-pregnane derivatives with LiAlH₄ gave the aziridines 13 and 16 , respectively. Their deamination led to the diene 14 and triene 17 , respectively. Reduction of isobutyl methyl ketone-oxime with LiAlH₄ in tetrahydrofuran yielded 2-amino-4-methyl-pentane ( 19 ) as main product, 1, 2-imino-4-methyl-pentane ( 22 ) as second product and the epimeric 2,3-imino-4-methyl-pentanes 20 and 21 as minor products. – 3β-Hydroxy-5-pregnen-20-one oxime ( 2 ) was transformed by methylmagnesium iodide in toluene to 20α, 21-imino-20-methyl-5-pregnen-3β-ol ( 23 ) and 20β, 21-imino-20-methyl-5-pregnen-3β-ol ( 26 ). Acetylation of these aziridines was accompanied by elimination reactions leading to 3β-acetoxy-20-methylidene-21-N-acetylamino-5-pregnene ( 30 ) and 3β-acetoxy-20-methyl-21-N-acetylamino-5,17-pregnadiene ( 32 ). The reaction of oxime 2 with ethylmagnesium bromide in toluene gave 20α, 21-imino-20-ethyl-5-pregnen-3β-ol ( 24 ) and 20α,21-imino-20-ethyl-5-pregnen-3β-ol ( 27 ). Acetylation of 24 and 27 led to 3β-acetoxy-20-ethylidene-21-N-acetylamino-5-pregnene ( 31 ), 3β-acetoxy-20-ethyl-21-N-acetylamino-5,17-pregnadiene 33 and 3β, 20-diacetoxy-20-ethyl-21-N-acetylamino-5-pregnene ( 37 ). With phenylmagnesium bromide in toluene the oxime 2 was transformed to 20β, 21-imino-20-phenyl-5-pregnen-3β-ol ( 25 ) and 20β,21-imino-20-phenyl-5-pregnen-3β-ol ( 28 ). Acetylation of 25 and 28 yielded 3β-acetoxy-20-phenyl-21-N-acetylamino-5, 17-pregnadiene ( 34 ) and 3β,20-diacetoxy-20-phenyl-21-N-acetylamino-5-pregnene ( 39 ). LiAlH₄-reduction of 39 gave 3β, 20-dihydroxy-20-phenyl-21-N-ethylamino-5-pregnene ( 41 ). – The 20, 21-aziridines are stable to LiAlH₄. Consequently they are no intermediates in the formation of the 20-amino derivatives obtained from the oxime 2 .     

云南美登木内生真菌Phomopsis sp. Lz42的化学成分

从云南美登木内生真菌Phomopsis species Lz42的琼脂平板发酵物中分离得到2个倍半萜和5个麦角甾醇类化合物(1~7), 其中化合物1和2为新化合物. 应用波谱技术确定其结构为4-Deacetyl-10-oxo-dihydrobotrydial(1)和麦角甾-6,22-二烯-5α,8α-环二氧-3-甲酸酯(2).     

Antibacterial compounds from Siraitia grosvenorii leaves

Luo Han Guo (LHG) fruits (Siraitia grosvenorii Swingle) have been used as traditional medicine in China for centuries to treat sore throats and coughs. However, LHG leaves are seldom used and minimal scientific information is available on them. In our recent study on the leaves of S. grosvenorii, the bioactive compounds β-amyrin (2), aloe emodin (5), aloe-emodin acetate (6), 5α,8α-epidioxy-24(R)-methylcholesta-6,22-dien-3β-ol (7) and p-hydroxyl benzyl acid (8), accompanied by n-hexadecaoic acid (1), 12-methyltetradecanoic acid (3), β-sitosterol (4) and daucosterol (9) were first obtained. Their structures have been identified on the basis of spectroscopic studies. The activities of these compounds were evaluated in?vitro against the growth of oral bacterial species Streptococcus mutans, Actinobacillus actinomycetemcomitans, Fusobacterium nucleatum and the yeast Candida albicans, and their minimum inhibition concentrations were determined. Furthermore, the activity against S. mutans is likely to be due to the inhibition of glucosyltransferase. The experimental data provide important information on bioactive phytochemicals in the leaf of S. grosvenorii, which shows that the leaf can be a new resource as an antibacterial agent.     

Simiranes A and B: erythroxylanes diterpenes and other compounds from Simira eliezeriana (Rubiaceae)

The first phytochemical study of Simira eliezeriana Peixoto (Rubiaceae) allowed the isolation and structural determination of two new diterpenes named simirane A [(5R,6R,8R,9R,10S,11S,13S)-6β,11β-dihydroxy-2,4(18),15-erythroxylatrien-1-one] (1) and simirane B [(5S,8R,9R,10S,11S,13S)-11β-hydroxy-2,4(18),15-erythroxylatrien-1-one] (2), together with seven known compounds: sitosterol (3), stigmasterol (4), campesterol (5), coniferaldehyde (6), vanillin (7), pinoresinol (8) and harman (9) from the bark of the plant. The structures of the compounds were established on the basis of spectroscopic methods, including 1-D and 2-D NMR, HRESI-MS and CD analysis and comparisons with available literature data of known compounds.     

Chemical constituents from the roots of Xanthium sibiricum

Xanthium sibiricum patrin ex Widder (Compositae) is an annual herb which grows all around China. Chemical investigations of its roots resulted in the identification of 15 compounds: stigmast-4-en-6β-ol-3-one (1), β-sitostenone (2), β-sitosterol (3), nonadecanoic acid (4), 5α,8α-epidioxy-22E-ergosta-6,22-dien-3β-ol (5), scopoletin (6), Jatrocin B (7), (±)syringaresinol (8), 9,9'-O-di-(E)-feruloyl-(-)-secoisolariciresinol (9), cleomiscosin A (10), cleomiscosin C (11), N-trans-feruloyl tyramine (12), daucosterol (13), 5-methyluracil (14) and uracil (15). Structures were elucidated by spectroscopic (NMR and MS) methods and confirmed by comparing with reference samples and literature data. Compounds 1-2, 4-12, 14, and 15 were isolated from this genus for the first time, while this is the first report of coumarinolignoids in the Compositae family, and coumarinoligoids could be considered as valuable chemotaxonomic markers for the plant.     

Inhibitory effects of constituents from Morus alba var. multicaulis on differentiation of 3T3-L1 cells and nitric oxide production in RAW264.7 cells

A new arylbenzofuran, 3',5'-dihydroxy-6-methoxy-7-prenyl-2-arylbenzofuran (1), and 25 known compounds, including moracin R (2), moracin C (3), moracin O (4), moracin P (5), artoindonesianin O (6), moracin D (7), alabafuran A (8), mulberrofuran L (9), mulberrofuran Y (10), kuwanon A (11), kuwanon C (12), kuwanon T (13), morusin (14), kuwanon E (15), sanggenon F (16), betulinic acid (17), uvaol (18), ursolic acid (19), β-sitosterol (20), oxyresveratrol 2-O-β-D-glucopyranoside (21), mulberroside A (22), mulberroside B (23), 5,7-dihydroxycoumarin 7-O-β-D-glucopyranoside (24), 5,7-dihydroxycoumarin 7-O-β-D-apiofuranosyl-(1→6)-O-β-D-glucopyranoside (25) and adenosine (26), were isolated from Morus alba var. multicaulis Perro. (Moraceae). Their structures were determined by spectroscopic methods. The prenyl-flavonoids 11-14, 16, triterpenoids 17,18 and 20 showed significant inhibitory activity towards the differentiation of 3T3-L1 adipocytes. The arylbenzofurans 1-10 and prenyl-flavonoids 11-16 also showed significant nitric oxide (NO) production inhibitory effects in RAW264.7 cells.     

Sesquiterpenes from the secondary metabolites of Streptomyces sp. (YIM 56130)

Three new sesquiterpenes were isolated from the fermentation broth of Streptomyces sp. and their structures were determined as caryolane-1,7α-diol (1), 1,6,11-eudesmanetriol; (1α,6β)-form (2), 11-eudesmene-1,6-diol; (1α,6β)-form (3), together with nine known compounds as caryolane-1,9α-diol (4), 2-methyl-5-nonanol (5), soyasaponin I (6), cyclo (Ala-Leu) (7), homononatinic acid (8), β-sitosteryl glucoside-3'-O-heptadecoicate (9), 2'-deoxythymidine (10), 2'-deoxyuridine (11), trehalose (12). The structures were elucidated by spectral analysis.     

Identification de stérols à chaînes latérales courtes dans l′éponge Damiriana hawaiiana

Identification of short side chain sterols in the sponge Damiriana hawaiiana The steroidal composition of the sponge Damiriana hawaiiana is examined. Twenty-seven components are identified. In addition to the C₂₆-C₂₉, Δ⁵-mono and diunsaturated sterols, the sponge contains sterols without side-chain: androsta-5, 16-dien-3β-ol( 1 ), androst-5-en-3β-ol( 2 ); sterols with a non-functionalized side-chain consisting of two, three, four, five and six carbon atoms: pregna-5, 20-dien-3β-ol( 5 ), pregn-5-en-3β-ol( 6 ), 23, 24-bisnor-chola-5, 20-dien-3β-ol( 7 ), 23, 24-bisnor-chol-5-en-3β-ol( 8 ), 24-nor-chol-5-en-3β-ol( 10 ), chol-5-en-3β-ol( 11 ), 26, 27-bisnor-cholest-5-en-3β-ol( 12 ), and sterols possessing a short oxygenated side-chain such as 3β-hydroxy-androst-5-en-17-one( 3 ), androst-5-en-3β, 17β-diol( 4 ) and 3β-hydroxy-26, 27-bisnor-22-trans-cholesta-5, 22-dien-24-one( 14 ). The probable biological or dietary origin rather than artifact production of these hitherto undescribed components from marine sources is supported by their relatively high concentration and their relative proportions, both very different from those expected for autoxidation.     

New Triterpenes from the Heartwood of Melaleuca leucadendron L.

Fourteen chemical constituents were isolated from the CHCl₃ soluble portion of the heartwood of Melaleuca leucadendron L. These compounds include β-sitosterol (1) , β-sitostenone (2) , 6-hydroxy-4,6-dimethyl-3-hepten-2-one (3) , naphthalene (4) , squalene (5) , 2α3β-dihydroxyurs-12-en-28-oic acid (6) , 3β-hydroxylup-20(29)-en-27,28-dioic acid (7) , 2α,3β-dihydroxyolean-12-en-28-oic acid (8) , 3β,23-dihydroxyolean-12-en-28-oic acid (9) , 2α,3β,23-trihydroxyolean-12-en-28-oic acid (10) , 3β-trans-p-coumaroyloxy-2α,23-dihydroxyolean-12-en-28-oic acid (11) , and three novel oleanane derivatives 23-trans-p-coumaroyloxy-2α,3β-dihydroxyotean-12-en-28-oic acid (12), 3β-trans-caffeoyloxy-2α,23-dihydroxyolean-12-en-28-oic acid (13) , and its isomer 3β-cis-caffeoyloxy-2α,23-dihydroxyolean-12-en-28-oic acid (14) , The three novel compounds were characterized as the two and three O-methylated derivatives, respectively.     

Reaktionen mit phosphororganischen Verbindungen. XLII. Nucleophile Substitutionen an Hydroxysteroiden mit Hilfe von Triphenylphosphan/Azodicarbonsäureester

Nucleophilic Substitution Reactions of Hydroxysteroids using Triphenylphosphane/diethylazodicarboxylate Nucleophilic substitution reactions by means of the title reagent on various more or less hindered steroid alcohols with suitable nucleophils in benzene is described. It was not possible to run this substitution process in the hitherto used solvent THF. Cholestan-3α-ol ( 1 ) was transformed to the 3β-substituted products 3β-benzoyloxy-cholestane ( 1a ) and 3β-azido-cholestane ( 1b ). Testosterone ( 2 ) affords with the corresponding nucleophils after short heating in benzene the inverted 17α-substituted products 3a, 3b and 3c . Analogously the 17α-azido-derivative 5a arises from 17β-hydroxy-androst-3-on ( 4 ). In the presence of a ketogroup in the substrate a competitive reaction can occur as it is shown in the case of cholestan-3-on ( 6 ): the products are the en-hydrazo-dicarboxylate-steroids 7a and 7b . The sterically very hindered 11α-position in 11α-hydroxy-4-pregnen-3,20-dion ( 8 ) can be transformed also to the 11β-azide 9a . The substitution of a 6 β-hydroxy group in androstane-3β, 6β, 17β-triol-3,17-diacetate ( 10 ) to the 6α-azide 11a affords the elimination product 12 as main component. Trans-diaxial vicinal diols such as cholestane-2β,3α-diol ( 13 ) give a mixture of the α- and β-oxiranes 14a and 14b .     

Sterols from Sargassum oligocystum, a brown algae from the Persian Gulf, and their bioactivity

Sargassum oligocystum (Heterokontophyta) is one of the most abundant algae distributed in the Persian Gulf. In this study, the cytotoxic effects of this algae on brine shrimp larvae were evaluated and the main sterols of the algae identified. Separation and purification of the compounds was carried out using silica gel column chromatography and HPLC to obtain eight pure compounds, 1-8. Structural elucidation of the constituents was based on the data obtained from (1)H-NMR, (13)C-NMR, HSQC, HMBC, DEPT and EI-MS. The compounds separated from S. oligocystum were identified as 22-dehydrocholesterol (1), cholesterol (2), fucosterol (3), 29-hydroperoxystigmasta-5,24(28)-dien-3β-ol (4), 24-hydroperoxy-24-vinylcholesterol (5), a mixture of 24(S)-hydroxy-24-vinylcholesterol (6) and 24(R)-hydroxy-24-vinylcholesterol (7), and ostreasterol (8) based on their spectral data and from comparison with those previously reported in the literature.     

New Sesquiterpene Alcohols from Galbanum Resin; the occurrence of C (10)-epi-sesquiterpenoids

(+)-β-Eudesmol (7), (+)-10-epi-elemol (8) , (?)-(Z)-dihydrofarnesol (3) , and an alcohol believed to be a guai-9-en-11-ol (4) have been isolated from Galbanum resin. Together with (-)-β-dihydroagarofuran (1) and epi-ligulyl oxide (13) (reported naturally occurring for the first time), 10-elemol (8) and 10-epi-junenol (2) involve the enantiomeric stereochemistry at C (10) compared with β-eudesmol 7 , and guaiol 5 , the major sesquiterpene alcohol of Galbanum.     

Asterosaponins isolated from the starfish Asterias amurensis

Three new asterosaponins 1-3 and four known saponins 4-7 have been isolated from the starfish Asterias amurensis LüTKEN. By means of high magnetic field 1D- and 2D-NMR ((1)H-(1)H correlation spectroscopy (COSY), total correlation spectroscopy (TOCSY), heteronuclear multiple quantum coherence (HMQC), heteronuclear single quantum coherence (HSQC), heteronuclear multiple bond correlation (HMBC), and nuclear Overhauser effect spectroscopy (NOESY)) and MS analyses, the chemical structures of new compounds were determined to be 6α-O-[β-D-fucopyranosyl-(1→2)-β-D-galactopyranosyl-(1→4)-[β-D-quinovopyranosyl-(1→2)]-β-D-quinovopyranosyl-(1→3)-β-D-galactopyranosyl]-5α-chol-9(11)-en-23-one-3β-yl sodium sulfate (1), 6α-O-[β-D-fucopyranosyl-(1→2)-β-D-galactopyranosyl-(1→4)-[β-D-quinovopyranosyl-(1→2)]-β-D-quinovopyranosyl-(1→3)-β-D-galactopyranosyl]-5α-cholesta-9(11),24-dien-23-one-3β-yl sodium sulfate (2), and 6α-O-[β-D-fucopyranosyl-(1→2)-β-D-galactopyranosyl-(1→4)-[β-D-quinovopyranosyl-(1→2)]-β-D-quinovopyranosyl-(1→3)-β-D-galactopyranosyl]-5α-cholest-9(11)-en-23-one-3β-yl sodium sulfate (3). In addition, the NMR data for known saponins 4-7 were completely assigned by extensive 2D-NMR analysis without chemical degradation.