Unusual Guaiane Sesquiterpenoids from Artemisia rupestris

Two new guaiane sesquiterpenoids, (1β,5β)‐1‐hydroxyguaia‐4(15),11(13)‐dieno‐12,5‐lactone ( 1 ) and 1,5‐epoxy‐4‐hydroxyguai‐11(13)‐en‐12‐oic acid ( 2 ), together with five known compounds, rupestonic acid ( 3 ), strobilactone A ( 4 ), antiquorin ( 5 ), isosclerone ( 6 ), and 5‐hydroxy‐2′,3′,4′,7,8‐pentamethoxyflavone ( 7 ), were isolated from a 95% EtOH extract of Artemisia rupestris. Compounds 1 and 2 are rare examples of guaiane sesquiterpenoids, incorporating a 12,5‐lactone group or featuring a 1,5‐epoxy ring, respectively. The structures of 1 and 2 were identified by various spectroscopic methods. Compounds 1, 4 , and 5 exhibited moderate cytotoxic activities against the human lung cancer 95‐D cell line with IC₅₀ values of 11.3, 19.8, and 34.5 μM , respectively.     

3-（CH2）nCO2C2H5-1,5-苯并硫氮杂的合成、晶体结构及抑真菌活性

为了寻找具有更高抗真菌活性的杂类化合物并对高活性的杂衍生物A进行构效关系研究,设计合成了38个3-(CH2)nCO2C2H5-1,5-苯并硫氮杂衍生物6和7(n=1,2),其结构经核磁共振波谱、质谱、红外光谱及元素分析等确证;并采用X射线单晶衍射技术测定了目标化合物的立体结构,发现其分子中的七元杂环是扭曲的船式构象.实验还考察了合成化合物的抑真菌活性,结果表明,当乙氧羰基烷基[(CH2)nCO2C2H5]在七元杂环的3位时杂的活性降低;将Lewis CeCl3.7H2O-NaI用于催化含硫化合物与α,β-不饱和酮的迈克尔加成反应,发现该催化剂能有效促进高位阻α,β-不饱和酮与邻氨基苯硫酚的迈克尔加成;同时研究了中间体5的分子内缩合反应,发现TiCl4是合成Schiff碱非常有效的促进剂.     

Sesquiterpenoids from the Fruits of Alpinia oxyphylla and Their Anti‐Acetylcholinesterase Activity

Fourteen sesquiterpenoids were isolated from the fruits of Alpinia oxyphylla Miq . Their structures were elucidated based on NMR analyses (¹H, ¹³C, DEPT, ¹H,¹H‐COSY, HMQC, HMBC, and NOESY) and identified as 12‐nornootkaton‐6‐en‐11‐one ( 3 ), (+)‐(3S,4aS,5R)‐2,3,4,4a,5,6‐hexahydro‐3‐isopropenyl‐4a,5‐dimethyl‐1,7‐naphthoquinone ( 5 ), nootkatene ( 6 ), 9β‐hydroxynootkatone ( 7 ), 2β‐hydroxy‐δ‐cadinol ( 8 ), 4‐isopropyl‐6‐methyl‐1‐tetralone ( 11 ), oxyphyllone E ( 12 ), oxyphyllone D ( 13 ), oxyphyllanene B ( 15 ), oxyphyllone A ( 16 ), oxyphyllol E ( 17 ), (9E)‐humulene‐2,3;6,7‐diepoxide ( 18 ), mustakone ( 20 ), and pubescone ( 21 ). Among them, 3 was a new norsesquiterpenoid, 8 was a new natural product, and 5, 6, 11, 20, 21 were isolated from A. oxyphylla for the first time. Twenty sesquiterpenoids, 1 – 5 and 7 – 21 , were investigated for their in vitro acetylcholinesterase (AChE) inhibitory activities, including previously isolated seven sesquiterpenoids from A. oxyphylla, (11S)‐12‐chloronootkaton‐11‐ol ( 1 ), (11R)‐12‐chloronootkaton‐11‐ol ( 2 ), nootkatone ( 4 ), oxyphyllenodiol A ( 9 ), oxyphyllenodiol B ( 10 ), 7‐epiteucrenone B ( 14 ), and alpinenone ( 19 ). TLC‐Bioautographic assay indicated that 1 – 4, 7, 14, 16, 18, 19 , and 21 displayed anti‐AChE activities at 10 nmol. Microplate assay confirmed that 19, 18, 16 , and 21 displayed moderate‐to‐weak anti‐AChE activities at the concentration of 100 μM , and 19 was the most potent inhibitor with an IC₅₀ value of 81.6±3.5 μM . The presence of anti‐AChE sesquiterpenoids in A. oxyphylla may partially support the traditional use of this fruit for the treatment of dementia.     

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).     

Characterization of Eight New Secondary Metabolites from the Mutant Strain G‐444 of Tubercularia sp. TF5

Eight new metabolites, including five new sesquiterpenoids, 10,11‐epoxyguaian‐10‐ol ( 1 ), 10,11‐epoxyguaian‐13‐ol ( 2 ), a new backbone sesquiterpene rearranged from guaiane ( 3 ), two 1,5 : 1,10‐disecoguaianes, 4 and 5 , two new dihydroisocoumarins, 7‐chloromellein‐4‐ol ( 6 ) and 7‐chloromellein‐5‐ol ( 7 ), and one new tetralone, 7‐chloroscytalone ( 8 ), were isolated from the mutant strain G‐444 of Tubercularia sp. TF5, an endophytic fungus of Taxus mairei, along with ten known compounds, 3,4‐dihydro‐4,8‐dihydroxy‐2H‐naphthalen‐1‐one ( 9 ), (3R,4S)‐4‐hydroxymellein ( 10 ), 5‐formylmellein ( 11 ), 5‐carboxymellein ( 12 ), sporogen‐AO1 ( 13 ), tuberculariols A ( 14 ) and B ( 15 ), hymatoxin E ( 16 ), 4‐oxo‐4H‐pyran‐3‐acetic acid ( 17 ), and penicillic acid ( 18 ). Their structures were elucidated by spectroscopic analyses including HR‐ESI‐MS, 1D‐ and 2D‐NMR (HMQC, HMBC, ¹H,¹H‐COSY and NOESY). The antimicrobial activities of 1 – 8 were evaluated, but none showed any substantial effect.     

Sesquiterpenoid derivatives from Ferula ferulaeoides [correction of ferulioides]. IV

Four novel prenyl-furocoumarin type sesquiterpenoid derivatives, 2,3-dihydro-7-hydroxy-2S*,3R*-dimethyl-3-[4,8-dimethyl-3(E),7-nonadie nyl]-furo[3,2-c]coumarin, 2,3-dihydro-7-hydroxy-2R*,3R*-dimethyl-3-[4,8-dimethyl-3(E),7-nonadie nyl]-furo[3,2-c]coumarin, 2,3-dihydro-7-hydroxy-2S*,3R*-dimethyl-3-[4-methyl-5-(4-methyl-2-furyl)- 3(E)-pentenyl]-furo[3,2-c]coumarin, and 2,3-dihydro-7-methoxy-2S*,3R*-dimethyl-3-[4,8-dimethyl-3(E),7-nonadie nyl]-furo]3,2-c]coumarin were isolated from the roots of Ferula ferulaeoides [corrected]. Their structures were established by detailed spectral analysis and the biosynthetic pathway leading to these prenyl-furocoumarin type sesquiterpenoids is proposed based on these structures.     

Two New Sesquiterpenes from Eupatorium lindleyanum

Various germacrane sesquiterpenes have been isolated from many species of the Eupatorium.In recent years these compounds have been increasing interest due to their insecticidal,cytotoxic,antitumor-promoting and insect-antifeedant activities1.In our present study,we have investigated the chemical constituents of Eupatorium lindleyanum DC.,which is a geo-authentic medicine of Jiangsu province.It is used as a antipyretic drug.Two novel germacrane sesquiterpenes(Figure1)were found by us from th…     

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...     

Pubescone,a Novel 11(7→6)Abeo‐14‐norcarabrane Sesquiterpenoid from Siegesbeckia pubescens

The phytochemical investigation of the aerial parts of Siegesbeckia pubescens L. yielded 16 sesquiterpenoids, including a novel 11(7→6)abeo‐14‐norcarabrane sesquiterpenoid, pubescone ( 1 ), and a new germacrane sesquiterpene, 5 . The molecular structures of the isolated compounds were elucidated on the basis of extensive spectroscopic analysis, including 1D‐ and 2D‐NMR.     

Sesquiterpenoid derivatives from Ferula ferulaeoides [correction of ferulioides]. V

Nine novel prenyl-dihydrofurocoumarin-type sesquiterpenoid derivatives, 2,3-dihydro-7-hydroxy-2R*,3R*-dimethyl-2-[4,8-dimethyl-3(E),7-nonadienyl]-furo[3,2-c]coumarin, 2,3-dihydro-7-hydroxy-2S*,3R*-dimethyl-2-[4,8-dimethyl-3(E),7-nonadien-6-onyl]-furo[3,2-c]coumarin, 2,3-dihydro-7-hydroxy-2S*,3R*-dimethyl-2-[4-methyl-5-(4-methyl-2-furyl)-3(E)-pentenyl]-furo[3,2-c]coumarin, 2,3-dihydro-7-hydroxy-2R*,3R*-dimethyl-2-[4-methyl-5- (4-methyl-2-furyl)-3(E)-pentenyl]-furo[3,2-c]coumarin, 2,3-dihydro-7-methoxy-2S*,3R*-dimethyl-2-[4,8-dimethyl-3(E),7-nonadienyl]-furo[3,2-c]coumarin, 2,3-dihydro-7-methoxy-2R*,3R*-dimethyl-2-[4,8-dimethyl-3(E),7-nonadienyl]-furo[3,2-c]coumarin, 2,3-dihydro-7-methoxy-2S*,3R*-dimethyl-2-[4,8-dimethyl-3(E),7-nonadien-6-onyl]-furo-[3,2-c]coumarin, and 2,3-dihydro-7-methoxy-2S*,3R*-dimethyl-2-[4-methyl-5-(4-methyl-2-furyl)-3(E)-pentenyl]-furo[3,2-c]coumarin, were isolated from the roots of Ferula ferulaeoides [corrected]. The structures were established by comprehensive spectral analysis. The biosynthetic pathway leading to these prenyl-furocoumarin-type sesquiterpenoids is proposed based on their structures.     

Seimatoric acid and colletonoic acid:Two new compounds from the endophytic fungi,Seimatosporium sp.and Colletotrichum sp.

A new metabolite,named seimatoric acid(1),representing a new oxobutanoic acid derivative has been isolated from Seimatosporium sp., in addition to four known compounds viz.,2-hydroxymethyl-4β,5α,6β-trihydroxycyclohex-2-enone(2),(-)-phyllostine(3),(+)-epiepoxydon(4) and(+)-epoxydon monoacetate(5).Similarly one new benzoic acid derivative,named colletonoic acid(6) was isolated from the ethyl acetate fraction of Colletotrichum sp.The structures of the new compounds were elucidated by detailed ~1 H NMR,~(13)C NMR,COSY,HMQC.HMBC spectroscopic analysis,and HR-E1-MS.Seimatoric acid(1)was also isolated from another taxonomical unidentified fungal strain 4295 in ourgroup.The structures of the known compounds were elucidated by their spectral data comparison to literature data.Preliminary studies showed that colletonoic acid(6) showed good antibacterial,antifungal,and antialgal activities.     

Bioactive Trichothecenes Produced by the Myrothecium sp. QB‐1

Three new simple trichothecenes, 15‐acetyltrichoverrol B ( 3 ), 13′‐acetyltrichoverrin B ( 5 ), and 6′‐dehydroxytrichoverrin B ( 6 ), along with five known trichothecenes trichodermadienediol B ( 1 ), trichoverrol B ( 2 ), trichoverrin B ( 4 ), and roridins A ( 7 ) and D ( 8 ), have been isolated from the liquid culture of Myrothecium roridum (strain no. QB‐1). The structures of the new compounds were established by comprehensive analysis of 1D‐ and 2D‐NMR data. All the compounds were evaluated for antifungal activity, only compounds 7 and 8 showed significant antifungal activity against the tested fungi (MIC ranged from 10 to 5 μg/ml).     

Sesquiterpenoids, alantolactone analogues, and seco-guaiene from the roots of Inula helenium

Three new sesquiterpenoids, a new unusual dimeric eudesmanolide, bialantolactone, a new nor-eudesmanolide, trinoralantolactone, and a new seco-guaiene, 7S,1(10)Z-4,5-seco-guaia-1(10),11-diene-4,5-dioxo, together with 13 known sesquiterpenoids, were isolated from the roots of Inula helenium. Their structures were elucidated by comprehensive spectroscopic analyses. The absolute configurations of bialantolactone and 7S,1(10)Z-4,5-seco-guaia-1(10),11-diene-4,5-dioxo were defined via the experimental and computational optical rotation and CD data. The plausible biosynthetic pathways to bialantolactone and 7S,1(10)Z-4,5-seco-guaia-1(10),11-diene-4,5-dioxo are discussed. 16 compounds were evaluated for their anti-bacterial activities against six bacteria.     

Alkaloid and Anthraquinone Derivatives Produced by the Marine‐Derived Endophytic Fungus Eurotium rubrum

Cultivation of the fungal strain Eurotium rubrum, an endophytic fungus that was isolated from the inner tissue of the semi‐mangrove plant Hibiscus tiliaceus, resulted in the isolation of one new dioxopiperazine alkaloid, 12‐demethyl‐12‐oxo‐eurotechinulin B ( 1 ), and one new anthraquinone derivative, 9‐dehydroxyeurotinone ( 2 ), together with ten known compounds including variecolorin J ( 3 ), eurotechinulin B ( 4 ), variecolorin G ( 5 ), alkaloid E‐7 ( 6 ), cryptoechinuline G ( 7 ), isoechinulin B ( 8 ), 7‐isopentenylcryptoechinuline D ( 9 ), 2‐O‐methyl‐9‐dehydroxyeurotinone ( 10 ), emodin ( 11 ), and emodic acid ( 12 ). The structures of the isolated compounds were determined by extensive analysis of their spectroscopic data as well as by comparison with literature reports. Some of the purified compounds were evaluated for antibacterial, antifungal, and cytotoxic activities.     

Two Halogenated Sesquiterpenoids from the Fruits of Alpinia oxyphylla

Two new halogenated eremophilane‐type sesquiterpenoids, (11S)‐ and (11R)‐12‐chloronootkaton‐11‐ol ( 1 and 2 , resp.), together with five known sesquiterpenoids, nootkatone ( 3 ), 7‐epiteucrenone B ( 4 ), oxyphyllenodiol A ( 5 ), oxyphyllenodiol B ( 6 ), and alpinenone ( 7 ), were isolated from the EtOH extract of the fruits of Alpinia oxyphylla Miq . The structures were elucidated based on the analyses of their spectroscopic data.     

Myrrhanolide D and Myrrhasin A,New Germacrane‐Type Sesquiterpenoids from the Resin of Commiphora opobalsamum

Two new germacrane‐type sesquiterpenoids bearing an epoxy ring, myrrhanolide D ( 1 ) and myrrhasin A ( 2 ), together with eight known compounds, 3 – 10 , were isolated from the resinous exudates of Commiphora opobalsamum. Their structures were elucidated based on the analyses of their spectroscopic data. The isolated compounds 1, 2, 6 , and 8 were evaluated for their cytotoxic activities against human prostate cancer DU145 and PC3 cells.     

Isolation and biological activity of new and known isolation and biological activity of new and known diterpenoids from Sideritis stricta Boiss. & Heldr

Nine known and one new ent-kaurene diterpenoid were isolated from the acetone extract of Sideritis stricta Boiss & Heldr. The new compound, identified as ent-1 beta-hydroxy-7 alpha-acetyl-15 beta,16 beta-epoxykaurane (1) by IR, 1D and 2D NMR techniques and mass spectra, was isolated along with sideroxol (2), 7-acetyl sideroxol (3), 7-epicandicandiol (4), linearol (5), ent-7 alpha,15 beta,18-trihydroxy-kaur-16-ene (6), ent-7 alpha-acetyl,15,18-dihydroxy-kaur-16-ene (7), foliol (8), sideridiol (9) and siderol (10). The antibacterial and antifungal activities of these compounds and the whole crude acetone extract were evaluated against E. coli, S. aureus, K. pneumeonia and C. albicans.     

珠子参化学成分分析

从珠子参根茎中分离得到7个化合物. 利用核磁共振、 质谱和红外等手段, 并结合其理化性质, 鉴定了其结构, 它们分别是24(R)-珠子参苷R1, 6-O-[β-D-吡喃葡萄糖基(1→2)-β-D-吡喃葡萄糖基]-20-O-[β-D-吡喃葡萄糖基(1→4)-β-D-吡喃葡萄糖基]-20(S)-原人参三醇、 6″-乙酰基-人参皂苷Rd、 人参皂苷Rf、 竹节参皂苷Ⅳa、 人参皂苷Rd和竹节参皂苷Ⅴ. 其中, 24(R)-珠子参苷R1和6-O-[β-D-吡喃葡萄糖基(1→2)-β-D-吡喃葡萄糖基]-20-O-[β-D-吡喃葡萄糖基(1→4)-β-D-吡喃葡萄糖基]-20(S)-原人参三醇为2个新化合物, 6″-乙酰基-人参皂苷Rd 和人参皂苷Rf为首次从珠子参根茎中得到.     

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.     

New triterpene aldehydes,lucialdehydes A-C,from Ganoderma lucidum and their cytotoxicity against murine and human tumor cells

Three new lanostante-type triterpene aldehydes, named lucialdehydes A-C (1-3), were isolated from the fruiting bodies of Ganoderma lucidum, together with ganodermanonol (4), ganodermadiol (5), ganodermanondiol (6), ganodermanontriol (7), ganoderic acid A (8), ganoderic acid B8 (9), and ganoderic acid C1 (10). The structures of the new triterpenes were determined as (24E)-3 beta-hydroxy-5 alpha-lanosta-7,9(11),24-trien-26-al (1), (24E)-3,7-dioxo-5 alpha-lanosta-8,24-dien-26-al (2), and (24E)-3 beta-hydroxy-7-oxo-5 alpha-lanosta-8,24-dien-26-al (3), respectively, by spectroscopic means. The cytotoxicity of the compounds isolated from the ganoderma mushroom was tested in vitro against Lewis lung carcinoma (LLC), T-47D, Sarcoma 180, and Meth-A tumor cell lines. Lucialdehydes B, C (2, 3), ganodermanonol (4) and ganodermanondiol (6) showed cytotoxic effects on tested tumor cells. Of the compounds, lucialdehyde C (3) exhibited the most potent cytotoxicity against LLC, T-47D, Sarcoma 180, and Meth-A tumor cells with ED(50) values of 10.7, 4.7, 7.1, and 3.8 microg/ml, respectively.