Two new furostanol saponins from Tribulus terrestris L.

<正>Two new furostanol glycoside,26-O-β-D-glucopyranosyl-(25S)-5α-furost-3β,22α,26-triol-3-O-β-D-rhamnopyranosyl-(1→2)-[β-D-glucopyranosyl-(1→4)]-β-D-galactopyranoside(1) and 26-O-β-D-glucopyranosyl-(25S)-5α-furost-20(22)-en-2α,3β,26-triol-3-O-β-D-glucopyranosyl-(1→2)-O-β-D-glucopyranosyl-(1→4)-β-D-galactopyranoside(2) were isolated fromthe fruits of Tribulus terrestris L.The structures of two new furostanol saponins were elucidated by spectroscopic methods.     

Two new steroidal alkaloids from Veratrum nigrum var. ussuriense

<正>Two new steroidal alkaloids,veraussines A(1) and B(2) were isolated from the roots and rhizomes of Veratrum nigrum var.ussuriense.Their structures were determined as N-(ethoxycarbonyl)- 1α,2β,3α,15α-tetrahydroxy-5β-jervanin- 12-en- 11-one(1) andN-(methoxycarbonyl)- 1α,2β,3α,15α-tetrahydroxy-5β-jervanin- 12-en- 11 -one(2) by spectroscopic analysis.     

宽叶秦岭藤根部的化学成分

通过正相和反相硅胶柱层析从宽叶秦岭藤根部乙醇提取物中分离纯化得到19个化合物,经波谱分析并结合化学方法鉴定了其结构,其中4个为新化合物,它们分别是3,5-二羟基二十烷酸羽扇豆醇酯(3),2-羟甲基-5-甲氧基苯基-O-β-D-吡喃葡萄糖甙(11),Δ5-孕甾烯-3β,20(S)-二醇-20-O-β-D-吡喃葡萄糖基(1→6)-β-D-吡喃葡萄糖甙(18,秦岭藤甙C)和Δ5-孕甾烯-3β,20(S)-二醇-3-O-β-D-吡喃葡萄糖基-20-O-β-D-吡喃葡萄糖基(1→6)-β-D-吡喃葡萄糖甙(19,秦岭藤甙D).     

齿叶橐吾中新吉马烷型倍半萜结构研究

菊科案吾属植物在我国约有100种,是民间广泛应用的中草药资源,具有清热解毒、抗菌消炎、化痰止咳、活血止痛等功效D‘．本文报道了通过反复柱层析（溶剂石油醚：丙酮体积比为10：1～3：I）和制备薄层层析（溶剂苯：丙酮体积比为5：1）从齿叶蠢吾（＊fggLggfgdentata）中分离得到的一新吉马烷型倍半储,命名为la,4卢,6a,10a一四羟基一3卢,sa,sa一三当归酸氧基吉马一11一烯一9一酮（1）．化合物1为无色胶体,卜」g＋3·2“（＊＊Q。,C几51）．其’H、”C＊＊R和＊＊＊T谱表明1中存在3个当归酸氧基,在FAB－MS谱中有连续失去463…     

防己叶菝葜中的一个新甾体皂甙

防己叶菝葜为百合科菝葜属植物(SmilaxmenispermoidesD.C.),分布在我国西北,西南地区,民间用于祛风除湿代替中药土伏苓(S.ChinaRaxb)^[1,2]。迄今未见其化学成分的报道,本文报道防己叶菝葜中一个新的甾体皂甙1的结构鉴定。     

屈螺酮分子中6β,7β-亚甲基结构的简便构建及屈螺酮的合成

设计了简便构建屈螺酮分子中6β,7β-亚甲基结构的合成路线,并合成了屈螺酮.以16β,16β-亚甲基-3-氧代-17α-孕甾-4,6-二烯-21,17-羰内酯为起始原料,依次经硼氢化钠还原、间氯过氧苯甲酸环氧化、氢化铝锂还原性开环、Simmons-Smith加成以及铬酐氧化等5步反应得到目标化合物屈螺酮.中间体4β,5...     

草玉梅中的化学成分

从草玉梅根部和地上部分甲醇提取物中分离到的8个化合物,其中三萜内酯(7)和三萜皂甙(8)为新化合物.     

Three new steroidal saponins from the rhizome of Paris polyphylla

A mixture of a pair of stereoisomeric new spirostanol saponins (1a and 1b) and a new cholestane saponin (2) were isolated from the rhizome of Paris pollyphylla Smith var. yunnanensis. Their structures were elucidated as (25R)-spirost-5-en-3beta, 7beta-diol-3-O-alpha-L-arabinofuranosyl-(1 --> 4)-[alpha-L-rhamnopyranosyl-(1 --> 2)]-beta-D-glucopyranoside (1a), (25R)-spirost-5-en-3beta, 7alpha-diol-3-O-alpha-L-arabinofuranosyl-(1 --> 4)-[alpha-L-rhamnopyranosyl-(1 --> 2)]-beta-D-glucopyranoside (1b) and 26-O-beta-D-glucopyranosyl-(25R)-Delta(5(6), 17(20))-dien-16, 22-dione-cholestan-3beta, 26-diol-3-O-alpha-L-arabinofuranosyl-(1 --> 4)-[alpha-L-rhamnopyranosyl-(1 --> 2)]-beta-D-glucopyranoside (2) by a combination of HR-ESI-MS, FAB-MS, 1D and 2D NMR techniques (including (1)H-NMR, (13)C-NMR, (1)H--(1)H COSY, HSQC, HMBC and NOESY).     

Spirostanol Sapogenins and Saponins from Convallaria majalis L. Structural Characterization by 2D NMR,Theoretical GIAO DFT Calculations and Molecular Modeling

Two new spirostanol sapogenins (5β-spirost-25(27)-en-1β,2β,3β,5β-tetrol 3 and its 25,27-dihydro derivative, (25S)-spirostan-1β,2β,3β,5β-tetrol 4) and four new saponins were isolated from the roots and rhizomes of Convallaria majalis L. together with known sapogenins (isolated from Liliaceae): 5β-spirost-25(27)-en-1β,3β-diol 1, (25S)-spirostan-1β,3β-diol 2, 5β-spirost-25(27)-en-1β,3β,4β,5β-tetrol 5, (25S)-spirostan-1β,3β,4β,5β-tetrol 6, 5β-spirost-25(27)-en-1β,2β,3β,4β,5β-pentol 7 and (25S)-spirostan-1β,2β,3β,4β,5β-pentol 8. New steroidal saponins were found to be pentahydroxy 5-O-glycosides; 5β-spirost-25(27)-en-1β,2β,3β,4β,5β-pentol 5-O-β-galactopyranoside 9, 5β-spirost-25(27)-en-1β,2β,3β,4β,5β-pentol 5-O-β-arabinonoside 11, 5β-(25S)-spirostan-1β,2β,3β,4β,5β-pentol 5-O-galactoside 10 and 5β-(25S)-spirostan-1β,2β,3β,4β,5β-pentol 5-O-arabinoside 12 were isolated for the first time. The structures of those compounds were determined by NMR spectroscopy, including 2D COSY, HMBC, HSQC, NOESY, ROESY experiments, theoretical calculations of shielding constants by GIAO DFT, and mass spectrometry (FAB/LSI HR MS). An attempt was made to test biological activity, particularly as potential chemotherapeutic agents, using in silico methods. A set of 12 compounds was docked to the PDB structures of HER2 receptor and tubulin. The results indicated that diols have a higher affinity to the analyzed targets than tetrols and pentols. Two compounds (25S)-spirosten-1β,3β-diol 1 and 5β-spirost-25(27)-en-1β,2β,3β,4β,5β-pentol 5-O-galactoside 9 were selected for further evaluation of biological activity.     

Two new isospirostanol sapogenins from Reineckia carnea

Two new isospirostanol sapogenins named(25R)-5β-spirostane-(1α,3α)-diol(1) and(25R)-5β-spirostane-(1α,2α,3α,4α)tetrol(2) were isolated from the whole herb of Reineckia camea(Andr.) Kunth.The structures of the sapogenins were elucidated bychemical and spectral methods.     

A new pyrrolidine derivative and steroids from an algicolous Gibberella zeae strain

A new pyrrolidine derivative, 3-hydroxy-5-(hydroxymethyl)-4-(4'-hydroxyphenoxy)pyrrolidin-2-one (1), and eight known steroids, (22E,24R)-7beta,8beta-epoxy-3beta,5alpha,9alpha-trihydroxyergosta-22-en-6-one (2, a reassigned structure of (22E,24R)-5alpha,6alpha-epoxy-3beta,8beta,14alpha-trihydroxyergosta-22-en-7-one), (22E,24R)-3beta,5alpha,9alpha-trihydroxyergosta-7,22-dien-6-one (3), (22E,24R)-3beta,5alpha-dihydroxyergosta-7,22-dien-6-one (4), (22E,24R)-ergosta-7,22-dien-3beta/,5alpha,6beta-triol (5), (22E,24R)-ergosta-5,22-dien-3beta-ol (6), (22E,24R)-5alpha,8alpha-epidioxyergosta-6,22-dien-3beta-ol (7), (22E,24R)-5alpha,8alpha-epidioxyergosta-6,9(11),22-trien-3beta-ol (8), and (22E,24R)-1(10 --> 6)-abeo-ergosta-5,7,9,22-tetraen-3alpha-ol (9), were isolated from the cultures of Gibberella zeae, an endophytic fungus isolated from the marine green alga Codium fragile. Their structures and relative stereochemistry were elucidated by 1D, 2D NMR and mass spectroscopic techniques. Compound 1 showed cytotoxicity against A-549 and BEL-7402 cell lines.     

Cytotoxic diterpenoids from Vietnamese medicinal plant Croton tonkinensis GAGNEP

Six new ent-kaurane-type diterpenoids were isolated from the leaves of the endemic Vietnamese medicinal plant Croton tonkinensis GAGNEP. (Euphorbiaceae) together with three known ent-11alpha-acetoxy-7beta,14alpha-dihydroxykaur-16-en-15-one (1), ent-kaur-16-en-15-one 18-oic acid (5) and ent-18-hydroxykaur-16-ene (7). Their structures were determined by spectroscopic analyses to be ent-7beta-acetoxy-11alpha-hydroxykaur-16-en-15-one (2), ent-18-acetoxy-11alpha-hydroxykaur-16-en-15-one (3), ent-11alpha-acetoxykaur-16-en-18-oic acid (4), ent-15alpha,18-dihydroxykaur-16-ene (6), ent-11alpha,18-diacetoxy-7beta-hydroxykaur-16-en-15-one (8), and ent-(16S)-1alpha,14alpha-diacetoxy-7beta-hydroxy-17-methoxykauran-15-one (14). ent-Kaurane-type diterpenoids from Croton tonkinensis 2-4, 6, and 9-13, were tested for toxicity in the brine shrimp lethality assay. Compounds 9, 10, and 12 demonstrated significant activity, compounds 2, 3, 6, and 11 showed weak activity, and compounds 4 and 13 were inactive.     

Complete (1)H and (13)C assignments of the four major saponins from Dioscorea villosa (wild yam)

Complete (1)H and (13)C spectral assignments for the four major steroidal saponins isolated by methanolic extraction of the roots of Dioscorea villosa, collected in North Carolina, United States (in summer and autumn), are presented in this paper. The structures were determined by a combination of (1)H, (13)C and 2D NMR techniques and were found to be ((3beta,25R)-26-(beta-D-glucopyranosyloxy)-22-methoxyfurost-5-en-3-yl-O-beta-D-glucopyranosyl-(1 --> 3)-O-beta-D-glucopyranosyl-(1 --> 4)-O-[alpha-L-rhamnopyranosyl-(1 --> 2)]-beta-D-glucopyranoside (1) (or methyl parvifloside), ((3beta,25R)-26-(beta-D-glucopyranosyloxy)-22 methoxyfurost-5-en-3-yl-O-alpha-L-rhamnopyranosyl-(1 --> 2)-O-[beta-D-gluco- pyranosyl-(1 --> 4)]-beta-D-glucopyranoside (2) (or methyl protodeltonin), (3beta,25R)-spirost-5-en-3-yl-O-beta-D-glucopy ranosyl-(1 --> 3)-O-beta-D-glucopyranosyl-(1 --> 4)-O-[alpha-L-rhamnopyranosyl-(1 --> 2)]-beta-D-glucopyranoside (3) (or Zingiberensis saponin I) and (3beta,25R)-spirost-5-en-3-yl-O-alpha-L-rhamnopyranosyl-(1 --> 2)-O-[beta-Ds-glucopyranosyl -(1 --> 4)]-beta-D-glucopyranoside (4) (or deltonin).     

Structures of new sesquiterpenoids from Farfarae Flos

Two new bisabolane-type sesquiterpenoids, (3R,4R,6S)-3,4-epoxybisabola-7(14),10-dien-2-one and (1R,3R,4R,5S,6S)-1-acetoxy-8-angeloyloxy-3,4-epoxy-5-hydroxybisabola-7(14),10-dien-2-one, and a new oplopane-type sesquiterpenoid, 14(R)-hydroxy-7beta-isovaleroyloxyoplop-8(10)-en-2-one, were isolated from Farfarae Flos along with three known compounds. The structures of these compounds were elucidated on the basis of spectroscopic evidence.     

Zum verhalten von steroiddienen gegenüber Pb(OAc)4-n(N3)n

The reaction of 7-dehydrocholesterylbenzoate with the title reagent at a temperature of ?20° yields 50% 1, 3β-benzoyloxy-5α,14α-diazidocholest-7-en-6-one, and 25% 2, 3β-benzoyloxy-5α- azido-cholest-7-en-6-one. Under the same conditions 3,5-cholestadiene yields 3α,6β-diazidocholest-4- ene (40%; 3) and 6β-azido-cholest-4-en-3-one (6%; 4). The structure elucidation of the compounds 1–4 is supported by spectroscopy.     

A new veratramine alkaloid from the bulbs of Fritillaria hupehensis

A new highly conjugated alkaloid of veratramine type, 225,25S,5α-veratramine-7(8),12(14)-diene-3β,13β,23β-triol-6-one (1), was isolated from the bulbs of Fritillaria hupehensis Hsiao et K.C. Hsia. Its structure was determined on the basis of spectroscopic evidences.     

Constructing conformationally constrained macrobicyclic musks

To investigate the structure-odor correlation of musks, (12R)-12-methyl-13-tridecanolide (1), a macrocyclic musk, and 13-tridecanolide, its non-musky demethyl analogue, were conformationally constrained by introduction of methylene bridges between C-3 and C-8 or C-9. These [7.5.1]- and [8.4.1]-macrobicycles were synthesized starting from bicyclo[5.3.1]undec-8-en-9-one (3) and bicyclo[4.3.1]dec-7-en-8-one (8), respectively, by a sequence consisting of catalytic hydrogenation, alpha-alkylation with a TBS-protected (tert-butyldimethylsilyl) hydroxy halide, acid-catalyzed cyclization, oxidative cleavage of the formed enol ether double bond, and subsequent reduction of the carbonyl group via its tosylhydrazone. The compound (1R,6R,9R)-(+)-6-methyl-4-oxa-bicyclo[7.5.1]pentadecan-3-one (22) was found to possess the most pronounced musk odor, and this was rationalized by a superposition analysis with the polycyclic aromatic musk odorant (4S,7R)-Galaxolide (2). In its (1S,6R,9S)-(+)-stereoisomer 23 as well as in (1S,6R, 10R)-(+)-6-methyl-4-oxabicyclo[8.4.1]-pentadecan-3-one (18) the (6R)-methyl group seems to hinder the interaction with the musk receptor, while the demethyl compounds 7 and 12 showed only very faint odors.     

Sesquiterpenoids from Curcuma wenyujin dreg and their biological activities

Four new sesquiterpenoids,4,8-dioxo-6β-hydroxyl-7β,1 1-epoxycarabrane(1),4,8-dioxo-6β-hydroxyl-7,1 1-epoxycarabrane(2),wenyujinins Q and R(3-4),and nine known sesquiterpenoids(5-13) were isolated from the Curcuma wenyujin(C wenyujin) dreg.Their structures and relative configurations were elucidated using 1D,2D NMR,and HR-ESI-MS data.All the compounds were isolated for the first time from the C.wenyujin dreg and evaluated for their antibacterial and antifungal activities.Compounds 3,5-8 exhibited strong broad-spectrum antifungal activities against tested nine pathogenic fungi.     

Evaluation of the antiviral and antimicrobial activities of triterpenes isolated from Euphorbia segetalis

A phytochemical reinvestigation of the whole plant of Euphorbia segetalis yielded five tetracyclic triterpenes: 3beta-hydroxy-cycloart-25-en-24-one (1), cycloart-25-ene-3beta,24-diol (2), cycloart-23-ene-3beta,25-diol (3), lanosta-7,9(11),24-trien-3beta-ol (4) and lanosta-7,9(11),24(31)-trien-3beta-ol (5). beta-acetoxy-cycloart-25-en-24-one (1a) and glutinol (6), lupenone (7), dammaranodienol (9), cycloartenol acetate (10), 24-methylenecycloartanol acetate (11) and beta-sitosterol (12), isolated previously, were evaluated for their antiviral activities against Herpes simplex virus (HSV) and African swine fever virus (ASFV). Lupenone exhibited strong viral plaque inhibitory effect against HSV-1 and HSV-2. The in vitro antifungal and antibacterial activities of la, cycloart-23-ene-3beta,25-diol, 3-acetate (3a) and 6-12 were also investigated.     

Studies on the constituents of solanaceous plants. (46). Steroidal glycosides from the fruits of Solanum anguivi

Three new glycosides named anguiviosides A-C were isolated from the fruits of Solanum anguivi and characterized as follows:3-O-beta-chacotrioside (1), 3-O-[4-O-maloyl-alpha-L-rhamnopyranosyl(1-->2)]-alpha-L-rhamnopyra nosyl(1-->4)-beta-D-glucopyranoside (2) and 3-O-alpha-L-rhamnopyranosyl(1-->2)-beta-D-xylopyranosyl(1-->3)]-beta-D-+ ++glucopyranoide (3), of (25R,26R)-spirost-5-en-3beta,26-diol.