Sesquiterpene lactones from Smyrnium cordifolium

In addition to previously obtained furanosesquiterpenes, two new eudesmanolides and a new glechomanolide were isolated from the fruits of Smyrnium cordifolium, while the roots gave two new eudesmanolides. The new compounds from the fruits were 1β-acetoxy-eudesman-4(15), 7(11)-dien-8,12-olide, 1β-acetoxy-8β-hydroxy-eudesman-4(15),7(11)-dien-8,12-olide, 1β,10α;4α,5β-diepoxy-8-hydroxy-glechomanolide, those obtained from the roots were smyrnicordiolide and the corresponding 8β-hydroxy derivative belonging to a new type of oxepine derivative.     

Glechomanolides and eudesmanolides from Smyrnium perfoliatum

In addition to five known sesquiterpenoids, six new compounds were isolated from Smyrnium perfoliatum. The new compounds were 1β-acetoxy-eudesma-3,7(11),8-trien-8,12-olide, 1β-acetoxyeudesma-4(15),7(11),8-trien-8,12-olide, 1β-10α;4α,5β-diepoxy-8β-isobutoxy-glechomanolide, 1β, 10α;4α,5β-diepoxy-8α-isobutoxy-glechomanolide, 1β,4α-dihydroxy-2α,3α-epoxy-eudesma-7(11),8-dien-8,12-olide, 1β,4α-dihydroxy-2α,3α-epoxy-8β-methoxy-eudesma-7(11)-en-8α,12-olide.     

Chemotaxonomic significance of lindenane sesquiterpenoid dimers and eudesmane sesquiterpenoids from Chloranthus henryi Hemsl. var. hupehensis (Pamp.) K. F. Wu

Seventeen known compounds were isolated from the 95% alcohol extract of the aerial parts of Chloranthus henryi Hemsl. var. hupehensis (Pamp.) K. F. Wu, including five lindenane sesquiterpenoid dimers (1–5) and twelve eudesmane sesquiterpenoids (6–17). In the present research, compounds 3 sarcaglabrin C, 6 neolitacumone C, 7 ent-Atractylenolide III and 8 dehydrocarissone were reported from the Chloranthus genus for the first time, and compounds 1 spicachlorantin B, 2 chloramultilide C, 4 shizukaol B, 5 japonicone C, 9 6α-hydroxyeudesma-4(15),7(11),8(9)-triene-12,8-olide, 10 ent-(3R)-3-hydroxyatractylenolide III, 11 8βH-hydroxyeudesma-4(14),7(11)-dien-12,8-olide, 12 lasianthuslactone A, 13 (5S,6R,8S,10R)-6-hydroxyeudesma-4(15),7(11)-diene-12,8-olide, 14 4β-hydroxy5α,8β(H)-eudesm-7(11)-en-8,12-olide, 15 4β,8β-dihydroxy-5α(H)-eudesm-7(11)-en-8,12-olide, 16 curcolonol and 17 1β, 8β-dihydroxyeudesm - 3,7(11)-dien-8α,12-olide were firstly isolated from the plant. Their structures were elucidated on the basis of extensive spectroscopic and chemical analyses. Moreover, the chemotaxonomic significance of the isolated compounds is discussed.     

Sesquiterpene lactones,flavonoids and anthraquinones from Asphodeline globifera and Asphodeline Damascena

The known compounds chrysoeriol, apigenin, luteolin, acacetin, scutellarein, 6-methoxyluteolin, apigenin 7-glucoside, luteolin 7-glucoside, esculetin, chrysophanol, asphodeline, mircocarpin, sitosterol, 1-β-acetoxyeudesman-4(15),7(11)dien-2α,12-olide and 1-β-acetoxy-8β-hydroxyeudesman-4(15),7(11)-dien-8α,12-olide were isolated from Asphodeline globifera and A. damascena. A new sesquiterpene lactone 1-β-acetoxy-8β-ethoxyeudesman-4(15),7(11)dien-8α, 12-olide was also characterized. These are the first reports of sesquiterpene lactones in Asphodeline and in the Liliaceae.     

Sesquiterpenoids from Curcuma wenyujin with anti-influenza viral activities

Five sesquiterpenoids, 1α,8α-epidioxy-4α-hydroxy- 5αH-guai-7(11),9-dien- 12,8-olide. (1), 8,9-seco-4β-hydroxy-1α,5βH-7(11)-guaen-8,10-olide (2), 8α-hydroxy-1α, 4β,7βH-guai-10(15)-en- 5β,8β-endoxide(3), 7β,8α-dihydroxy-1α,4αH-guai-10(15)-en-5β,8β-endoxide(4) and 7-hydroxy-5(10),6,8-cadinatriene-4-one(5), together with seven known analogs were isolated from the rhizomes of Curcuma wenyujin. Their structures and relative configurations were determined on the basis of spectroscopic methods including 2D NMR techniques, and the structures of 1 and 2 were confirmed by single-crystal X-ray diffraction experiment. Compounds 1–10 and 12 showed significant in vitro antiviral activity against the influenza virus A with IC₅₀ values ranged from 6.80 to 39.97 μM, and SI values ranged from 6.35 to 37.25.     

Microbial transformation of neoandrographolide by Mucor spinosus (AS 3.2450)

Microbial transformation of neoandrographolide (1), was performed by Mucor spinosus (AS 3.2450). Ten metabolites were obtained and identified as 14-deoxyandrographolide (2), 17,19-dihydroxy-8,13-ent-labdadien-16,15-olide (3), 3,14-dideoxyandrographolide (4), 7β-hydroxy-3,14-dideoxyandrographolide (5), 17,19-dihydroxy-7,13-ent-labdadien-16,15-olide (6), 8(17),13-ent-labdadien-16,15-olid-19-oic acid (7), 8α,17β-epoxy-3,14-dideoxyandrographolide (8), 8β,17,19-trihydroxy-ent-labd-13-en-16, 15-olide (9), phlogantholide-A (10), 19-[(β-d-glucopyranosyl)oxy]-19-oxo-ent-labda-8(17),13-dien-16,15-olide (11) by spectroscopic and chemical means. Among them, products 3, 5, 6, 8 and 9 were characterized as new compounds. The inhibitory effects of compounds 1–11 on nitric oxide production in lipopolysaccharide-activated macrophages were evaluated and their preliminary structure–activity relationships (SAR) were discussed.     

Two new sesquiterpenes from Ligularia dictyoneura

The detailed investigation of the whole plant of Ligularia dictyoneura was performed during a search for unique chemical skeletons. One novel noreremophilane-type sesquiterpene, (4S, 5R, 8R, 10S)-1-nor-10-hydroxy-8-methoxyeremophil-7(11)-en-12,8-olide (1) and one new highly oxygenated eremophilane, 1β-angeloyloxy-6α, 10β-dihydroxyeremophil-7(11), 8-dien-12, 8-olide (2), were obtained. Their structures, including the absolute configuration, were elucidated by spectroscopic data and CD analysis.     

Eudesmane-type sesquiterpenes from the liverwort Apomarsupella revolute

Phytochemical investigation of the Et₂O extract of liverwort Apomarsupella revolute led to isolation and identification of five new eudesmane-type sesquiterpenoids, 6β-hydroxy-9β-acetoxy-eudesma-4,11-dien (1), 6β-hydroxy-9β-acetoxy-eudesma-4,11-dien-3-one (2), 5α,6β-dihydroxy-9β-acetoxy-eudesma-4(15),11-dien (3) 4β-hydroxy-9β-acetoxy-11,12,13-trinor-5-eudesmen-7-one (4) and 4β-methox-9β-acetoxy-11,12,13-trinor-5-eudesmen-7-one (5), two of which were trinorsesquiterpenoids. Their structures were established unequivocally on the basis of spectroscopic data analysis. All compounds were preliminary bioscreened for their cytotoxicities and antifungal activities.     

Cytotoxic sesquiterpene lactones from Artemisia anomala

Two new sesquiterpene lactones, 8α-acetoxy-1,10α-epoxy-2-oxo-guaia-3,11(13)-dien-12,6α-olide (1) and 13-acetoxy-1-oxo-4α-hydroxy-eudesman-2(11)-dien-12,6α-olide (2), along with six known analogs (3-8), were isolated from the whole plant of Artemisia anomala S. Moore. Their structures were elucidated by extensive analysis of spectroscopic data. Compounds 6 and 7 exhibited in vitro moderate cytotoxicity against A549 cells with IC₅₀ values of 0.6 and 0.9 μM, and HepG2 cells with IC₅₀ values of 5.4 and 3.0 μM, respectively.     

Microbial transformation of 3β-acetoxypregna-5,16-diene-20-one by Penicillium citrinum

The biotransformation of 3β-acetoxypregna-5,16-diene-20-one (1) by using a filamentous fungus Penicillium citrinum resulted in the production of four metabolites 2–5. The structures of these compounds were elucidated by different spectroscopic analysis (1D- and 2D-NMR) and HR-ESI-MS as 3β,7β-dihydroxy-pregn-5,16(17)-dien-20-one (2), 3β-hydroxy-7α-methoxy-pregn-5,16(17)-dien-20-one (3), 3β,7β,11α-trihydroxy-pregn-5,16(17)-dien-20-one (4), and a known 3β,7α-dihydroxy-pregn-5,16(17)-dien-20-one (5). The 7-O-methylation is a novel reaction in the field of microbial transformation of pregnane steroids.     

Cucurbitane-type triterpenoids from the aerial parts of Momordica charantia L.

Six new cucurbitane-type triterpenoids (1–6), together with two known analogues (7 and 8) were isolated from the aerial parts of Momordica charantia L. The structures of new compounds were identified as cucurbita-6,24-dien-3β,23-diol-19,5β-olide (1), (19R)-5β,19-epoxy-19-methoxycucurbita-6,24-dien-3β,23-diol (2), (19S)-5β,19-epoxy-19-methoxycucurbita-6,24-dien-3β,23-diol (3), (19R)-5β,19-epoxy-19-isopropoxycucurbita-6,24-dien-3β,23-diol (4), 3β,23-dihydroxy-5-methoxycucurbita-6,24-dien-19-al (5) and (19R)-7β,19-epoxy-19-methoxycucurbita-5,24-dien-3β,23-diol (6), by extensive MS, 1D and 2D NMR spectroscopic technologies. This is the first report of the isolation of tetracyclic triterpenoids possessing a 7β,19-epoxy system, viz., 6, from M. charantia L.     

Guaianolides and elemanolides from Vernonia anthelmintica

Two new guaianolides, (1R,4R,5S,6R,7R,8S)-8,15-dihydroxyguaia-10(14),11(13)-dien-12,6-olide (1) and (1R,4R,5S,6R,7R,8S,11S)-8,15-dihydroxyguaia-10(14)-en-6,12-olide (2), and two known elemanolides, (4S,5R,6R,7R,8S,10R,11S)-11,13-dihydrovernolepin (3) and (5R,6R,7R,8S,10R,11S)-melitensin (4) were isolated from the aerial parts of Vernonia anthelmintica Willd. The structures of these compounds were determined on the basis of IR, UV, MS, 1D-NMR and 2D-NMR, and their absolute configurations were deduced using the CD exciton chirality method and single-crystal X-ray diffraction. The possible biosynthetic relationships of compounds 1–4 are postulated. Compounds 1–4 were evaluated for their cytotoxicity against HL-60 and SMMC-7721 cell lines.     

Biotransformation of dianabol with the filamentous fungi and β-glucuronidase inhibitory activity of resulting metabolites

Biotransformation of the anabolic steroid dianabol (1) by suspended-cell cultures of the filamentous fungi Cunninghamella elegans and Macrophomina phaseolina was studied. Incubation of 1 with C. elegans yielded five hydroxylated metabolites 2–6, while M. phaseolina transformed compound 1 into polar metabolites 7–11. These metabolites were identified as 6β,17β-dihydroxy-17α-methylandrost-1,4-dien-3-one (2), 15α,17β-dihydroxy-17α-methylandrost-1,4-dien-3-one (3), 11α,17β-dihydroxy-17α-methylandrost-1,4-dien-3-one (4), 6β,12β,17β-trihydroxy-17α-methylandrost-1,4-dien-3-one (5), 6β,15α,17β-trihydroxy-17α-methylandrost-1,4-dien-3-one (6), 17β-hydroxy-17α-methylandrost-1,4-dien-3,6-dione (7), 7β,17β,-dihydroxy-17α-methylandrost-1,4-dien-3-one (8), 15β,17β-dihydroxy-17α-methylandrost-1,4-dien-3-one (9), 17β-hydroxy-17α-methylandrost-1,4-dien-3,11-dione (10), and 11β,17β-dihydroxy-17α-methylandrost-1,4-dien-3-one (11). Metabolite 3 was also transformed chemically into diketone 12 and oximes 13, and 14. Compounds 6 and 12–14 were identified as new derivatives of dianabol (1). The structures of all transformed products were deduced on the basis of spectral analyses. Compounds 1–14 were evaluated for β-glucuronidase enzyme inhibitory activity. Compounds 7, 13, and 14 showed a strong inhibition of β-glucuronidase enzyme, with IC₅₀ values between 49.0 and 84.9 μM.     

New derivatives from the aerial parts of Boerhaavia diffusa L. (Nyctaginaceae)

Boerhaavia diffusa L. is used in the traditional medicine of several Asian countries. The isolation and identification of five new compounds, together with 11 known compounds, from the ethyl acetate extract of the aerial part of B. diffusa grown Vietnam is reported. The structure of the new compounds was established by 1D and 2D NMR spectroscopy, and high resolution ESI-MS analysis. New compounds are two rotenoids: 9,11-dihydroxy-6,10-dimethoxy[1]benzopyrano[3,4-b][1]benzopyran-12(6H)-one (boeravinone P, 3) and 3-[2-(β-d-glucopyranosyloxy)-3-hydroxyphenyl]-5-hydroxy-2-hydroxymethyl-7-methoxy-6-methyl-4H-1-benzopyran-4-one (boeravinone Q, 9), an atropisomeric mixture of two rotenoid glycosides (3′,5-dihydroxy-2-hydroxymethyl-7-methoxy-6-methylisoflavone 2′-O-β-d-glucopyranoside, 11), a sesquiterpene lactone (4,10-dihydroxy-8-methoxyguai-7(11)-en-8,12-olide, 5) and a new phenylpropanoid glycoside (boerhaavic acid, 15).     

Rare hydroperoxyl guaianolide sesquiterpenes from Pulicaria undulata

Pulicaria species, such as Pulicaria undulata, are rich in sesquiterpene lactones. The methylene chloride/methanol (1:1) extract of P. undulata resulted in the isolation of new sesquiterpenes (1–4), as well as previously reported metabolites (5–14). Structures were elucidated by spectroscopic analyses. Using a mouse peritoneal macrophage bioassay, lipopolysaccharide-induced nitric oxide inhibition was observed with the eudesman-type sesquiterpene 1β,4β-dihydroxy-5αH,7αH,8α-guaia-10(14),11(13)-dien-8β,12-olide (11) at an EC₅₀ of 7.2 μM.     

多穗金栗兰中一个新的酚苷

从多穗金粟兰(Chloranthus multistachys)全株的甲醇提取物中分离得到1个新的酚苷,通过波谱技术鉴定其结构为丁香酸-4-O-a-L-鼠李吡喃糖苷(1).同时还首次从该植物中分离得到两个已知倍半萜内酯和一个已知木脂素:1β,4β-二羟基-5a,8β-二氢-7(11)Z-桉叶烯-8,12-内酯(2),lβ,4a-二羟基-5a,8β-二氢-7(11)Z-桉叶烯-8,12-内酯(3),(-)-(7S,8R)-dihydrodehydrodiconifery alcohol(4).     

Triterpenoids from Mallotus repandus: Three new δ-lactones

The leaves of Mallotus repandus contain friedelin, 3β-hydroxy-13α-ursan-28,12β-olide (1), its benzoate (2) and ursolic acid. The stems contain friedelin, lupeol, α-amyrin, 2 and 3α-hydroxy-13α-ursan-28, 12β-olide (3), 21α-hop-22(29)-ene-3β,30-diol and ursolic acid. 1–3 are new compounds.     

New sesquiterpene lactones from Inula oculus-christi L.

Investigation of the aerial parts of Inula oculus-christi L. led to the identification of four new sesquiterpene lactones: an eudesmanolide (4α,15α-epoxypulchellin E) and three guaianolides (2α-acetoxy-4α,9β-dihydroxy-1β-guaia-11(13),10(14)-dien-12,8α-olide, 9β,10β-epoxygaillardin, 9α,10α-epoxy-2-epi-gaillardin), in addition to the known gaillardin, pulchellin E, pulchellin C and 3-O-palmitates of 16β-hydroxylupeol, 16β-hydroxy-β-amyrin, and faradiol. The structures of all compounds have been elucidated on the basis of their spectral data.     

Triterpenoid profile and bioactivity study of Oenothera maritima

Four new triterpenoids, 2α,3α,20β,23-tetrahydroxy-ursa-12,19(29)-dien-28-oic acid (1), 2α,3α,20β,23-tetrahydroxy-ursa-12,19(29)-dien-28,20β-lactone (2), 2α,3α-dihydroxy-ursa-12,19-dien-28-oic acid 28-O-β-d-glucopyranoside (3) and 2α,3α,23-trihydroxy-ursa-12,19(29)-dien-28-oic acid (4) together with six known compounds (5–10), were isolated from the aerial parts of Oenothera maritima Nutt. Their structures were elucidated on the basis of spectroscopic data and chemical methods. Compounds 1, 3–10 were evaluated for their in vitro thrombin inhibitory activity and their selectivity against factor Xa and trypsin.