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.     

Separation and Determination of Eremophilenolides from Ligulariopsis shichuana by Capillary Zone Electrophoresis

A new method of capillary zone electrophoresis (CZE) was established by simultaneous assay of four eremophilenolides, 3β-acetoxy-9β-angeloyloxy-1β,10β-epoxy-8α-hydroxyeremophil-7(11)-en-8β (12)-olide (1), 3β-senecioyloxy -1β,10β-epoxy-8α-hydroxyeremophil-7(11)-en-8β (12)-olide (2), 6α-hydroxy-1β,10β-epoxy-8α-hydroxyeremophil-7(11)-en-8β (12)-olide (3) and 3β-acetoxy- 6β-angeloyloxy-1β,10β-epoxy-8α-hydroxyeremophil-7(11)-en-8β (12)-olide (4) in the Chinese herbal extract from Ligulariopsis shichuana. The optimum buffer system was 20 mM borate buffer (pH 10.00). Voltage was 25 kV and detection at 214 nm. Regression equations revealed linear relationships (correlation coefficients 0.9986, 0.9990, 0.9992 and 0.9995) between the peak area of each compound and its concentration. The relative standard deviations of migration times and peak areas were <1.35 and 3.94% within 1 day, respectively. The effects of several CE parameters on the resolution were studied systematically. The contents of four eremophilenolides in Ligulariopsis shichuana were successfully determined with satisfactory repeatability and recovery.     

Terpenoids from Turraeanthus species

Chemical investigation of the root bark of Turraeanthus mannii and the stem of T. longipes resulted in the isolation of two new diterpenes, 13-methyl-labda-8(17)-en-15-oic acid (1) and 13-(hydroxymethyl)-14-hydroxy-ent-labda-8(17)-en-15-oic acid (2), along with two known diterpenes, 19-hydroxy-ent-labda-8(17),13-dien-15,16-olide (3) and 19-acetoxy-ent-labda-8(17),13-dien-15,16-olide (4), and the phytosterol, stigmasterol. The structure elucidation of the new compounds has been achieved using spectroscopic techniques.     

Eremophilane sesquiterpenes from the endophytic fungus Xylaria sp. GDG-102

A new eremophilane sesquiterpene, xylareremophil (1), together with five known eremophilanes, 1α,10α-epoxy-3α-hydroxyeremophil-7(11)-en-12,8β-olide (2), 1,10α,13-trihydroxyeremophil-7(11)-en-12,8-olide (3), 1α,10α-epoxy-13-hydroxyeremophil-7(11)-en-12,8β-olide (4), mairetolides B (5) and G (6) were isolated from the endophytic fungus Xylaria sp. GDG-102 cultured from Sophora tonkinensis. Their structures were elucidated on the basis of spectroscopic data analysis. The absolute configurations of 1 was determined by comparing computed electronic circular dichroism (ECD) and optical rotation (OR) with experimental results. Compounds 1, 5 and 6 showed antibacterial activities against Proteus vulgaris, Micrococcus luteus, Micrococcus lysodeikticus and Bacillus subtilis with MIC values of 25–100 μg/mL.     

Norlanostane and lanostane glycosides from the bulbs of Chionodoxa luciliae and their cytotoxic activity

Ten lanostane glycosides (1-10), including two new norlanostane glycosides (2 and 7) and a new lanostane glycoside with a spirolactone ring system (9), were isolated from the fresh bulbs of Chionodoxa luciliae (Liliaceae). The structures of the new compounds were determined on the basis of extensive spectroscopic analysis and the results of hydrolytic cleavage to be (23S)-3beta-[(O-beta-D-apiofuranosyl-(1-->2)-O-[beta-D-glucopyranosyl-(1-->3)]-O-beta-D-glucopyranosyl-(1-->2)-alpha-L-arabinopyranosyl-(1-->6)-beta-D-glucopyranosyl)oxy]-17alpha,23-epoxy-28,29-dihydroxy-27-norlanost-8-en-24-one (2), (23S)-17alpha,23-epoxy-29-hydroxy-3beta-[(O-alpha-L-rhamnopyranosyl-(1-->2)-O-[O-beta-D-glucopyranosyl-(1-->2)-beta-D-glucopyranosyl-(1-->3)]-O-beta-D-glucopyranosyl-(1-->2)-alpha-L-arabinopyranosyl-(1-->6)-beta-D-glucopyranosyl)oxy]-27-norlanost-8-ene-15,24-dione (7), and (23S,25R)-17alpha,23-epoxy-29-hydroxy-3beta-[(O-alpha-L-rhamnopyranosyl-(1-->2)-O-[beta-D-glucopyranosyl-(1-->3)]-O-beta-D-glucopyranosyl-(1-->2)-alpha-L-arabinopyranosyl-(1-->6)-beta-D-glucopyranosyl)oxy]lanost-8-en-23,26-olide (9), respectively. The cytotoxic activity of the isolated compounds against HSC-2 human oral squamous cell carcinoma cells are also reported.     

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.     

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.     

大叶橐吾中三个新的艾里莫芬型倍半萜

从大叶橐吾的根部分离得到三个新的艾里莫芬型倍半萜(1, 2和3), 经多种波谱方法和单晶X射线衍射确定它们的结构分别为: 6α,15β-环氧-8β-羟基-艾里莫芬-7(11)-烯-8α,12-内酯(1), 7-乙酰基-13β-羧酸-6(7)-烯-降-艾里莫芬烷(2), 艾里莫芬-7(11)-烯-6α,15β-内酯(3). 此外, 对化合物1进行了抗菌和抗癌活性测试.     

A Chemical Study of Burley Tobacco Flavour (Nicotiana tabacum L.) VII. Identification and synthesis of twelve irregular terpenoids,related to solanone,including 7,8-dioxabicyclo[3.2.1]octane and 4,9-dioxabicyclo[3.3.1]nonane derivatives

Twelve novel constituents isolated from Burley tobacco condensate by semi-preparative GLC. have been identified as (E)-3,4-epoxy-5-isopropyl-nonane-2,8-dione ( A ), exo-(1-methyl-4-isopropyl-7,8-dioxabicyclo[3.2.1]oct-6-yl)methyl ketone ( B ), exo-1-(1-methyl-4-isopropyl-7,8-dioxabicyclo[3.2.1]oct-6-yl)-ethanol ( C ), (E)-5-isopropyl-8-hydroxy-8-methyl-non-6-en-2-one ( D ), (E)-5-isopropyl-6,7-epoxy-8-hydroxy-8-methyl-nonan-2-one ( E ), endo-2-(1-methyl-4-isopropyl-7,8-dioxabicyclo[3.2.1]oct-6-yl)-propan-2-ol ( F ), 3,3,5-trimethyl-8-isopropyl-4,9-dioxabicyclo[3.3.1]nonan-2-ol ( G ), (E)-5-isopropyl-non-3-ene-2,8-diol ( H ), 5-isopropyl-nonane-2,8-diol ( I ), (E)-5-isopropyl-8-hydroxy-non-6-en-2-one ( J ), 5-isopropyl-8-hydroxy-nonan-2-one ( K ), and (E)-3-isopropyl-6-methyl-hepta-4,6-dien-1-ol ( L ). Compounds A–K were synthesized from norsolanadione ( 2 ), and compound L from 2-isopropyl-5-oxo-hexanal ( 15 ). The relative configuration of the bicyclic internal acetals B, C, F, G and their δ-keto-epoxide precursors A and E is discussed. All these Burley tobacco flavour components belong to a growing family of metabolites structurally related to solanone ( 1 ). They are believed to arise from the breakdown of cembrene-type precursors.     

Antitrypanosomal activity of a novel norlignan purified from Nectandra lineata

Bioactivity-guided fractionation of a MeOH-EtOAc extract from the young leaves of Nectandra lineata (Lauraceae), using a Trypanosoma cruzi bioassay resulted in the isolation of a novel norlignan 3'-methoxy-3,4-methylenedioxy-4',7-epoxy-9-nor-8,5'-neolignan-9'-acetoxy (1), together with the known compound, 3'-methoxy-3,4-methylenedioxy-4'-7-epoxy-9-nor-8,5'-neolignan-7,8'-diene (2). Compounds 1 and 2 were shown to inhibit the growth of T. cruzi epimastigotes in axenic culture.     

Chemical constituents from Farfugium japonicum var. formosanum

Two new eremophilenolides, 6beta,8beta,10beta-trihydroxyeremophil-7(11)-en-12,8-olide (1) and 3beta-acetoxy-8alpha-hydroxy-6beta-methoxyeremophila-7(11),9-dien-12,8-olide (2) along with twenty-nine other compounds were obtained from the methanolic extracts of the aerial parts and rhizomes of Farfugium japonicum (L.) Kitam. var. formosanum (Hayata) Kitam. (Compositae = Asteraceae). The structures of the isolated compounds were characterized and identified by spectral techniques. Compounds 5, 6, 10, 12-24, 29, and 30, were reported for the first time from this genus. Cytotoxicity and anti-inflammatory activity of the isolated compounds were evaluated. Compounds 3 and 16 possessed moderate cytotoxicity against human breast cancer cell line (MCF 7). Compounds 3, 16, 25 and 26 exhibited moderate cytotoxicity against hepatoma cells (Hep G2 and Hep 3B). With respect to the anti-inflammatory activity, compounds 15 and 16 (each 10 microg/mL) inhibited superoxide anion generation by human neutrophils in response to fMLP/CB by 92.0% and 87.3%, respectively.     

千里光中四个新倍半萜的结构

从植物千里光中分得四个新艾里莫芬烷型倍半萜,经仔细的波谱分析和单晶X射线衍射,研究它们的结构分别为为：7β,11-环氧-9α,10α-环氧-8-羰基艾里莫芬烷(1),8-11-过氧-9α,10α-环氧-6-烯-8β-羟基艾里莫芬烷(2),7(11)-烯-9α,10α-环氧-8-羰基艾里莫芬烷(3),6-烯-9α,10α-环氧-11-羟基-8-羰基艾里莫芬烷(4)。活性筛选实验表明化合物1具有促进癌细胞生长作用,化合物2和3具有较好的抗癌活性。     

A New Xanthanolide from Carpesium longifolium

A new xanthanolide was isolated from the aerial parts of Carpesium longifolium.It‘‘‘‘‘‘‘‘s structure was elucidated as 1β,4β-epoxy-5β-hydroxy-10αH-xantha-11(13)-3n-12,8β-olide by spectral methods(HRMS,1D and 2D NMR).     

Structure of new carotenoids with a 3,4-dihydroxy-beta-end group from the oyster Crassostrea gigas

Three new carotenoids with a 3,4-dihydroxy-beta-end group were isolated from the oyster Crassostrea gigas. These structures were determined to be 3,4,3',8'-tetrahydroxy-beta,kappa-caroten-6'-one (1), 3,4-dihydroxy-3',6'-epoxy-1',2',5',6'7',8'-hexahydro-6'-methyl-16'-nor-beta,-carotene-1',8'-dione (2), and 3,6-epoxy-5,3',4'-trihydroxy-12',13',20'-trinor-beta,beta-caroten-19,11-olide (3) based on chemical and spectral data.     

Pulchellin C and inuchinenolide C from Inula caspica

The pseudoguaianolide inuchinenolide C and the eudesmanolide pulchellin C have been isolated for the first time from the flower heads and leaves ofInula caspica Blume, and their spatial structures have been established by an x-ray structural experiment as 2α,6β-diacetoxy-6α-hydroxy-1α,7α(H),8β,10β(H)-pseudoguai-11(13)-en-8,12-olide and 2α,3β-dihydroxy-5β,7α,8α(H)-eudesma-4(15),11(13)-dien-8,12-olide, respectively.     

Constituents of Clinopodium Umbrosum

The isolation and identification of fifteen crystalline components from the whole herb of Clinopodium umbrosum (Bieb.) C. Koch (Labiatae) are described. Their structures were determined on the basis of spectral evidence and chemical transformation. These compounds include five steroids (α-spinasterone, β-sitosterol, stigmasterol, α-spinasterol, and α-spinasteryl-3-O-β-glucopyranoside), four triterpenoids (3β-hydroxyurs-11-en-28,13-olide, betulinic acid, oleanolic acid, ursolic acid), four flavonoids (luteolin, luteolin-7-O-β-glucopyranoside, apigenin-7-O-β-glucuronide, and apigenin-7-O-β-methylglucuronate), and two lignolic acids [3-(3,4-dihydroxyphenyl)- lactic acid and rosmarinic acid].     

Nucleophilic Substitution in the Allylic System of Codeine and Pseudocodeine: Reactions with lithium cyano(methyl)-and (aryl)cyanocuprates. Crystal and molecular structure of 8α-phenyl-6,7-didehydro-4,5α-epoxy-3-methoxy-17-methylmorphinan and 6α-phenyl-7,8-didehydro-4,5α-epoxy-3-methoxy-17-methylmorphinan

Nucleophilic substitution of 6β-chloro-7,8-didehydro-4,5α-epoxy-3-methoxy-17-methylmorphinan ( 1 ) and 8α-bromo-6,7-didehydro-4,5α-epoxy-3-methoxy-17-methylmorphinan ( 2 ) with lithium cyano(methyl)- and (aryl)cyanocuprates(I) ( 5a–c ) was accompanied by allylic rearrangement with both change and retention of orientation of the substituting group (Scheme 1, Table 1). Nucleophilic substitution in 7,8-didehydro-4,5α-epoxy-3-methoxy-17-methylmorphinan-6α-yl methanesulfonate ( 3 ) and 7,8-didehydro-4,5α-epoxy-3-methoxy-17-methylmorphinan-6β-yl methanesulfonate ( 4 ) proceeded without allylic rearrangement with both change and retention of the orientation of the substituting group (Scheme 2, Table 1). X-Ray diffraction studies of the products 6,7-didehydro-4,5α-epoxy-3-methoxy-17-methyl-8α-phenylmorphinan ( 6b ) and 7,8-didehydro-4,5α-epoxy-3-methoxy-17-methyl-6β-phenylmorphinan ( 7b ) were carried out (Figs. 1 and 2).     

Total synthesis of two γ-butyrolactone containing compounds (Z,11S)-3,4-trans-11-hydroxy-3-methyldodec-cis-6-en-4-olide and (Z)-3,4-trans-11-oxo-3-methyldodec-cis-6-en-4-olide

The first total synthesis of (Z,11S)-3,4-trans-11-hydroxy-3-methyldodec-cis-6-en-4-olide and (Z)-3,4-trans-11-oxo-3-methyldodec-cis-6-en-4-olide was accomplished using Jacobsen hydrolytic kinetic resolution, Ohira–Bestmann reaction, regioselective alkyne addition to terminal carbon atom of epoxide, intramolecular TEMPO/BAIB mediated oxidative lactonization and partial hydrogenation as the key steps.     

Identification of Twenty-one Novel Constituents of Oriental Tobacco Flavour (Nicotiana tabacumL.) including (E)-3-methyl-non-2-en-4-one,pentadecan-15-olide, 8α, 13:9α, 13-diepoxy-15, 16-dinorlabdane, (Z)-octadec-9-en-18-olide,and (E)-2-ethylidene-6, 10, 14-trimethyl-pentadecanal

Investigation by gas liquid chromatography of a small but organoleptically typical subfraction of Oriental tobacco condensate led to the identification of 47 compounds. Of these 21 have hitherto not been reported as Oriental tobacco constituents, and 14 appear to be novel to all tobacco types. The latter are (E)-3-methyl-non-2-en-4-one ( 1 ), (E)-1-(2, 3, 6-trimethylphenyl)-but-2-en-1-one ( 3 ), pentadecan-15-olide ( 12 ), 8α, 13:9α, 13-diepoxy-15, 16-dinorlabdane ( 17 ), (Z)-octadec-9-en-18-olide ( 18 ), (E)-2-ethylidene-6, 10, 14-trimethylpentadecanal ( 21 ), the norlabdanoids 9 , 10 , 11 , 14 , 15 , 16 , tridecan-2-one, and 2-phenylethyl isovalerate. The macrolides 12 and 18 represent the first musk compounds detected in tobacco. Identification were made by direct comparison (MS. and/or ¹ H-NMR./IR.) with the authentic chemicals synthesized whenever necessary.     

Two New Diterpenoids from Hedychium forrestii

Two new labdane diterpenes isolated from the rhizomes of Hedychium forrestii were determined by spectroscopic evidence to be labda-8(17), 11, 13-trien-7β-hydroxyl- 15(16)-olide (1,hedyforrestin B) and labda-8(17), 11, 13-trien-7β,16-dihydroxyl-16(15)-olide (2, hedyforrestinC).