Clerodane diterpenoids from Microglossa angolensis

Two new diterpenoids, 6β-(2-methylbut-2(Z)-enoyl)-3α,4α,15,16-bis-epoxy-8β,10βH-ent-cleroda-13(16),14-dien-20,12-olide and 10β-hydroxy-6-oxo-3α,4α,15,16-bis-epoxy-8βH-cleroda-13(16),14-dien-20,12-olide, together with the known β-amyrin, spinasterol, 5,7-dihydroxy-3,8,3′,4′-tetramethoxyflavone and 5,7-dihydroxy-3,8,3′,4′,5′-pentamethoxyflavone have been isolated from the aerial parts of Microglossa angolensis Oliv. et Hiern (Compositae). The structures were elucidated on the basis of spectral studies and comparison with published data.     

海枫藤中C21甾体苷的分离和结构测定

从萝摩科植物海枫藤[Marsdenia officinalis Tsiang et P.T.Li.]的藤茎中分离得到四个C21甾体去氧糖苷(1)～(4). 通过化学降解和波谱技术, 确定它们的化学结构依次为: 12-O-桂皮酰基-20-O-乙酰基(20S)-孕甾烷-6-烯-3β,5α,8β,12β,14β, 17β,20-庚醇 3-O-甲基-6-去氧-β-D-阿洛吡喃糖基-(1→4)-β-D-夹竹桃吡喃糖基-(1→4)-β-D-磁麻吡喃糖苷(1), 12-O-桂皮酰基-20-O-乙酰基(20S)-孕甾烷-6-烯-3β,5α,8β,12β,14β,17β,20-庚醇3-O-β-D-葡萄吡喃糖基-(1→4)-3-O-甲基-6-去氧-β-D-阿洛吡喃糖基-(1→4)-β-D-磁麻吡喃糖基-(1→4)-β-D-磁麻吡喃糖苷(2), 12-O-桂皮酰基-20-O-乙酰基(20S)-孕甾烷-6- 烯-3β,5α,8β,12β,14β,17β,20-庚醇3-O-β-D-黄夹吡喃糖基-(1→4)-β-D-磁麻吡喃糖基-(1→4)-β-D-磁麻吡喃糖苷(3), 12-O-烟酰基-肉珊瑚苷元3-O-β-D-葡萄吡喃糖基-(1→4)-3-O-甲基-6-去氧-β-D-阿洛吡喃糖基-(1→4)-β-D-夹竹桃吡喃糖基- (1→4)-β-D-磁麻吡喃糖基-(1→4)-β-D-磁麻吡喃糖苷(4). 其中1和2为新化合物, 分别命名为haifengtenoside A, haifengtenoside B, 3和4分别为已知化合物mucronatoside H 和 hainaneosides A, 系首次从该植物中分离得到.     

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.     

Sesquiterpenoids from Costus Root Oil (Saussurea lappa CLARKE)

Apart from the well-known constituents (+)-β-selinene ( 2 ), (?)-β-elemene ( 4 ), (+)-β-costol ( 7 ), (?)-caryophyllene ( 17 ), and (?)-elemol ( 19 ) the following sesquiterpenoids have been isolated for the first time from costus root oil (Saussurea lappa CLARKE ): (?)-α-selinene ( 1 ), (+)-selina-4, 11-diene ( 3 ), (?)-α-trans-bergamotene ( 5 ), (?)-α-costol ( 6 ), (+)-γ-costol ( 8 ), (?)-elema-1,3,11 (13)-trien-12-ol ( 9 ), (?)-α-costal ( 11 ), (+)-γ-costal ( 12 ), (+)-γ-costal ( 13 ), (?)-elema-1,3,11 (13)-trien-12-al (elemenal, 14 ), (?)-(E)-trans-bergamota-2, 12-dien-14-al ( 15 ), (?)-ar-curcumene ( 16 ), and (?)-caryophyllene oxide ( 18 ). Compounds 6 , 8 , 9 , and 13 are new sesquiterpenoids. IR. and NMR. spectra of 12 sesquiterpenoids are reproduced.     

Synthesis of the 2,5-dioles of A-nor-5-alpha-cholestanes and A-nor-5-beta-cholestanes

Treatment of A-nor-Δ³⁽⁵⁾-cholestene-2-one ( 1 ) with alkaline hydrogen peroxide gave 3β,5-epoxy-A-nor-cholestane-2-one ( 2 ) and the epoxylactone 3 (BAEYER -VILLIGER reaction). LiAlH₄-reduction of 2 yielded A-nor-5β-cholestane-2β,5-diol( 4 ) (main product) and A-nor-5β-cholestane-2α,5-diol ( 5 ). LiAlH₄-reduction of 1 led mainly to A-nor-Δ³⁽⁵⁾-cholestene-2α-ol ( 8 ). Catalytic hydrogenation of 8 gave the known A-nor-5α-cholestane-2α-01 ( 10 ), A-nor-5β-cholestane-2α-01 ( 11 ) (main product), A-nor-5β-cholestane ( 9 ) and A-nor-5β-cholestane-2-one ( 12 ). By LiAlH₄-reduction of the ketones 12 and 13 the two additional alcohols 14 and 15 were obtained.     

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.     

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 .     

Novel Sesquiterpenoids from Siegesbeckia orientalis

Five new sesquiterpenoids, namely, 8β‐(angeloyloxy)‐4β,6α,15‐trihydroxy‐14‐oxoguaia‐9,11(13)‐dien‐12‐oic acid 12,6‐lactone ( 1 ), 4β,6α,15‐trihydroxy‐8β‐(isobutyryloxy)‐14‐oxoguaia‐9,11(13)‐dien‐12‐oic acid 12,6‐lactone ( 2 ), 11,12,13‐trinorguai‐6‐ene‐4β,10β‐diol ( 3 ), (1(10)E,4E,8Z)‐8‐(angeloyloxy)‐6α,15‐dihydroxy‐14‐oxogermacra‐(1(10),4,8,11(13)‐tetraen‐12‐oic acid 12,6‐lactone ( 9 ), and (1(10)E,4β)‐8β‐(angeloyloxy)‐6α,14,15‐trihydroxygermacra‐1(10),11(13)‐dien‐12‐oic acid 12,6‐lactone ( 11 ), and three new artifacts, (1(10)E,4Z)‐8β‐(angeloyloxy)‐9α‐ethoxy‐6α,15‐dihydroxy‐14‐oxogermacra‐1(10),4,11(13)‐trien‐12‐oic acid 12,6‐lactone ( 6 ), (1(10)E,4Z)‐8β‐(angeloyloxy)‐9α,13‐diethoxy‐6α,15‐dihydroxy‐14‐oxogermacra‐1(10),4‐dien‐12‐oic acid 12,6‐lactone ( 7 ), and (1(10)E,4Z)‐8β‐(angeloyloxy)‐9α‐ethoxy‐6α,15‐dihydroxy‐13‐methoxy‐14‐oxogermacra‐1(10),4‐dien‐12‐oic acid 12,6‐lactone ( 8 ), together with the three known sesquiterpenoids 4, 5 , and 10 , were isolated from the aerial parts of Siegesbeckia orientalis L. Their structures were established by spectral methods, especially 1D‐ and 2D‐NMR spectral methods.     

Ceramide and Cerebroside from the stem bark of Ficus mucuso (Moraceae)

Two new sphingolipids mucusamide (1) and mucusoside (2) have been isolated from methanol soluble part of the stem bark of Ficus mucuso WELW., together with fifteen known secondary metabolites including cellobiosylsterol (3), β-sitosterol (4), stigmasterol (5), β-sitosterol 3-O-β-D-glucopyranoside (6), lupeol acetate (7), ursolic acid (8), procatechuic acid (9), 2-methyl-5,7-dihydroxychromone 8-C-β-D-glucoside (10), apigenin (11), (-)-epicatechin (12), (+)-catechin (13), N-benzoyl-L-phenylalanilol (14), α-acetylamino-phenylpropyl α-benzoylamino-phenylpropionate (15), asperphenamate (16) and bejaminamide (17). Structures of compounds 1 and 2 were elucidated by spectroscopic analysis and chemical methods.     

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.     

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.     

Synthetic transformations of isoquinoline alkaloids. Synthesis of 1-halo derivatives of <Emphasis Type="Italic">endo</Emphasis>-ethenotetrahydrothebaine and their behavior in the heck reaction

Bromination of endo-ethenotetrahydrothebaine derivatives having a pyrrolidine ring fused at the C⁷-C⁸ bond, namely 1′-substituted 4,5α-epoxy-6α,14-etheno-3,6-dimethoxy-17-methyl-2′,5′,7β,8β-tetrahydro-1′H-14α-pyrrolo[3′,4′:7,8]morphinan-2′,5′-diones, 1′-aryl-4,5α-epoxy-6α,14-etheno-3,6-dimethoxy-17-methyl-2′,5′,7β,8β-tetrahydro-1′H-14α-pyrrolo[3′,4′:7,8]morphinans, and 4,5α-epoxy-6α,14-etheno-2′α-hydroxy-3,6-dimethoxy-17-methyl-1′-phenyl-2′,5′,7β,8β-tetrahydro-1′H-14α-pyrrolo[3′,4′:7,8]morpphinan-5′-one, with molecular bromine in formic acid smoothly afforded the corresponding 1-bromo derivatives. Iodination of 4,5α-epoxy-6α,14-etheno-3,6-dimethoxy-17-methyl-1′-phenyl-2′,5′,7β,8β-tetrahydro-1′H-14α-pyrrolo[3′,4′:7,8]-4,5α-epoxy-6α,14-etheno-3,6-dimethoxy-17-methyl-1′-phenyl-2′,5′,7β,8β-tetrahydro-1′H-14α-pyrrolo[3′,4′:7,8]-morphinan-2′,5′-dione with iodine(I) chloride gave 4,5α-epoxy-6α,14-etheno-1-iodo-3,6-dimethoxy-17-methyl-1′-phenyl-2′,5′,7β,8β-tetrahydro-1′H-14α-pyrrolo[3′,4′:7,8]morphinan-2′,5′-dione. The resulting 1-halo derivatives were brought into the Heck reaction with acrylic acid esters to obtain 1-[(E)-2-(alkoxycarbonyl)ethenyl]-substituted compounds. Demethylation of the 6-methoxy group in 1-bromo-endo-ethenotetrahydrothebaines was accomplished using boron(III) bromide in chloroform.     

Terpene glycosides from the roots of Sanguisorba officinalis L. and their hemostatic activities

Guided by a hemostasis bioassay, seven terpene glycosides were isolated from the roots of Sanguisorba officinalis L. by silica gel column chromatography and preparative HPLC. On the grounds of chemical and spectroscopic methods, their structures were identified as citronellol-1-O-α-L-arabinofuranosyl-(1→6)-β-D-glucopyranoside (1), geraniol-1-O-α-L-arabinofuranosyl-(1→6)-β-D-glucopyranoside (2), geraniol-1-O-α-Larabinopyranosyl-(1→6)-β-D-glucopyranoside (3), 3β-[(α-L-arabinopyranosyl)oxy]-19α-hydroxyolean-12-en-28-oic acid 28-β-D-glucopyranoside (4), 3β-[(α-L-arabinopyranosyl)-oxy]-19α-hydroxyurs-12-en-28-oic acid 28-β-D-glucopyranoside (ziyu-glycoside I, 5), 3β,19α-hydroxyolean-12-en-28-oic acid 28-β-D-glucopyranoside (6) and 3β,19α-dihydroxyurs-12-en-28-oic acid 28-β-D-glucopyranoside (7). Compound 1 is a new mono-terpene glycoside and compounds 2, 3 and 5 were isolated from the Sanguisorba genus for the first time. Compounds 1–7 were assayed for their hemostatic activities with a Goat Anti-Human α2-plasmin inhibitor ELISA kit, and ziyu-glycoside I (5) showed the strongest hemostatic activity among the seven terpene glycosides. This is the first report that ziyu-glycoside Ι has strong hemostatic activity.     

藤黄化学成分的研究

传统中药藤黄通过各种色谱方法分离纯化, 得到15个化合物, 根据其理化性质和光谱方法鉴定其结构分别为: 2α-羟基-3β-乙酰氧基白桦酯酸(1), 10α-羟基表藤黄酸(2), 藤黄酸(3), 异藤黄酸(4), gambogin (5), gambogoic acid B (6), desoxymorellin (7), isomorellin (8), gambogenic acid (9), isogambogenin (10), gambogellic acid (11), desoxygambogenin (12), morellic acid (13), isomorellic acid (14), 30-hydroxygambogic acid (15). 其中化合物1和2为新化合物.     

Chemical constituents and antibacterial activity of Melastoma malabathricum L

The aqueous methanolic extracts of Melastoma malabathricum L. exhibited antibacterial activity when assayed against seven microorganisms by the agar diffusion method. Solvent fractionation afforded active chloroform and ethyl acetate fractions from the leaves and the flowers, respectively. A phytochemical study resulted in the identification of ursolic acid (1), 2α-hydroxyursolic acid (2), asiatic acid (3), β-sitosterol 3-O-β-D-glucopyranoside (4) and the glycolipid glycerol 1,2-dilinolenyl-3-O-β-D-galactopyanoside (5) from the chloroform fraction. Kaempferol (6), kaempferol 3-O-α-L-rhamnopyranoside (7), kaempferol 3-O-β-D-glucopyranoside (8), kaempferol 3-O-β-D-galactopyranoside (9), kaempferol 3-O-(2″,6″-di-O-E-p-coumaryl)-β-D-galactopyranoside (10), quercetin (11) and ellagic acid (12) were found in the ethyl acetate fraction. The structures of these compounds were determined by chemical and spectral analyses. Compounds 1-4, the flavonols (6 and 11) and ellagic acid (12) were found to be active against some of the tested microorganisms, while the kaempferol 3-O-glycosides (7-9) did not show any activity, indicating the role of the free 3-OH for antibacterial activity. Addition of p-coumaryl groups results in mild activity for 10 against Staphylococcus aureus and Bacillus cereus. Compounds 2-5, 7 and 9-12 are reported for the first time from M. malabathricum. Compound 10 is rare, being reported only once before from a plant, without assignment of the double bond geometry in the p-coumaryl moiety.     

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).     

arabinonucleosides

The α-D-arabinonucleosides of cytosine ( 6 ) and 5-fluorouracil ( 9 ) were prepared from the 2,3,-5-tri-O-benzoyl-D-arabinofuranosyl halides, in keeping with the trans rule. The 2′-O-methyl-)3-D-arabinonucleosides of 5-fluorouraeil (β- 14 ) and adenine (β- 21a ) were prepared from 3,5-di-O-(4-ehlorobenzoyl)-2-O-methyl-α-D-arabinofuranosyl chloride, although in both cases a lesser amount of the α-anomer was also found. Reaction of 3,5-di-O-(4-chlorobenzoyl)-2-deoxy-2-(methylthio)-α-D-arabinofuranosyl chloride, prepared in four steps from methyl 2,3-anhydro-α-D-ribofurano-side ( 15 ), with N-benzoyladenine gave slightly more of the β- than the α-arabinonucleoside 20b . The β-anomer was converted to 9-[2-deoxy-2-(methylthio)-β-D-arabinofuranosyl]adenine. Only 1-α-D-arabinofuranosylcytosine ( 6 ) proved to be cytotoxic.     

Constituents of Fruit Bodies of Tramete orientalis

A known sterol, 5α,6α-epoxy-5α-crgosta-8(14),22E-diene-3β,7α-diol ( 1 ), and two new sterols, 5α,6α-epoxy-3β,8β,14α-trihydroxy-5α-ergost-22E-en-7-one ( 2 ), (3α,5α),(8β,11β)-diepidioxy-ergost-22E-en-12-one ( 3 ), were isolated and characterized from dried fruit bodies of Trametes orientalis. Their structures were elucidated according to spectral methods.     

The synthesis of β-heteroarylamino-α,β-dehydro-α-amino acid derivatives via thiazolones

2-Alkoxy-4-heteroarylaminomethylene-5(4H)-thiazolones 4 were converted with various nucleophiles into β-heteroarylamino-α,β-dehydro-α-amino acid derivatives 11, 14, 15, 16, 17, 18 , and 19 . Reduction of 4 with sodium borohydride in ethanol saturated with gaseous ammonia afforded the corresponding β-heteroaryl-amino substituted alanyl amides 20 . Thiazoledione derivative 7a was transformed with sodium methoxide in methanol into 1-(4,6-dimethylpyrimidinyl-2)-4-mercaptocarbonylimidazol-2(3H)-one ( 8a ).     

Study on the phenolic constituents of the flowers and leaves of Trifolium repens L

The flowers and leaves of Trifolium repens L. (Fabaceae) were subjected to phytochemical investigation in order to identify their major chemical constituents and to evaluate in?vitro antioxidant activity of the isolated compounds against DPPH˙. A total of 12 flavonoids, pterocarpan and methyl caffeate were isolated, then characterised by UV, MS, NMR spectroscopy and identified as quercetin and kaempferol 3-O-(6″-α-rhamnopyranosyl-2″-β-xylopyranosyl)-β-galactopyranosides (1, 2), kaempferol 3-O-(2″,6″-α-dirhamnopyranosyl)-β-galactopyranoside, mauritianin (3), quercetin and kaempferol 3-O-(2″-β-xylopyranosyl)-β-galactopyranosides (4, 5), kaempferol and quercetin 3-O-β-(6″-O-acetyl)-galactopyranosides (6, 7), trifolin (8), hyperoside (9), myricetin 3-O-β-galactopyranoside (10), quercetin (11), ononin (12), medicarpin 3-O-β-glucopyranoside (13) and methyl caffeate (14). Mauritianin, ononin, pterocarpan and methyl caffeate have been reported in this plant for the first time. The compounds 4, 7, 9, 10, and 11 were tested for their antioxidant effect against DPPH˙. All studied compounds were found to have potent activity, but the most effective in the test were compounds 9, 10 and 11 (EC(50) values in the range 7.51-9.52?μM).