Three verrucosane diterpenoids,verrucosane triol and related compounds from the liverwort Mylia verrucosa

Three new diterpenoids of the verrucosane class were isolated as minor constituents of the methanol extract of the liverwort Mylia verrucosa and their structures shown to be 2β,9α,13β-trihydroxyverrucosane,9α-acetoxy-2β,13β-dihydroxyverrucosane and 2β,13β-dihydroxy-9-oxoverrucosane.     

佛司可林类成分的光谱特征(一)

活性二萜佛司可林和异佛司可林已从毛喉鞘蕊花分离得到。本文详细描述了它们的光谱特征(包括一维和二维的核磁共振谱)。     

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.     

Diterpenoids of Halimium viscosum

From the neutral fraction of the hexane extract of Halimium viscosum the following components were isolated; 7-labdene-3β,l5-diol, 15-acetoxy-7-labden-3β-ol and a new diterpene-lactone with a rearranged ent-labdane skeleton, 13S-ent-9, 1-friedo-labd-1(10)-en-15-acetoxy-2R,18-olide. From the non-saponifiable part, beside 7-labdene-3β, 15-diol and 7, 13E-labdadiene-3β, 15-diol, the new diterpene 8(17)-labdene-3β, 7α, 15-triol was extracted. The structures were elucidated by spectroscopic methods, correlations or synthesis.     

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.     

Diterpenoids from galeopsis angustifolia

The structures of two new diterpenoids, galeopsin and pregaleopsin, isolated from aerial parts of Galeopsis angustifolia (Labiatae) have been shown to be 8β-acetoxy-15,16-epoxy-9α-hydroxylabda-13(16),14-dien-7-one and 8β-acetoxy-9α,13R; 15,16-diepoxylabd-14-en-7-one, respectively, by chemical and spectroscopic studies. The previously known diterpenoid hispanolone (15,16-epoxy-9α-hydroxy-8α-labda-13(16),14-dien-7-one) has been also obtained from the same source. A thermal retroaldol reaction in the absence of solvent experienced by these 9-hydroxy-7-keto-labdanes is also described.     

Two new triterpenoids from Rhodomyrtus tomentosa

Repetition of an investigation of the petrol extracts of Rhodomyrtus tomentosa has led to the isolation of two new triterpenoids, R₄ from the leaves and R₅ from the stems besides R₁, R₂, R₃ and the other known compounds already reported. R₁ and R₄ were proved to be 21α$\text{H}$-hop-22(29)en-3β,30-diol and 3β-hydroxy-21α$\text{H}$-hop-22(29)-en-30-al respectively, and R₂, R₃ and R₅ are 3β-acetoxy-11α,12α-epoxyoleanan-28,13β-olide, 3β-acetoxy-12α-hydroxyoleanan-28, 13β-olide and 3β-acetoxy-12-oxo-oleanan-28,13β- olide respectively. The ethanol extract of the leaves contained betulinic, ursolic and aliphitolic acids and that of the stems betulonic, betulinic and oleanolic acids.     

New diterpenes from Sideritis canariensis

Two new diterpenes ribenol [3α-hydroxy-(?)-13-epimanoyl oxide] (I)and 7β-acetoxy-18-hydroxytrachylobane (IX) as well as the known (?)-13-epimanoyl oxide (IV) have been isolated from Sideritis canariensis Ait.     

Eudesmane sesquiterpenoid lactones and abietane diterpenoids from Ajuga forrestii Diels

Four eudesmane sesquiterpenoid lactones (1–4) and seven abietane diterpenoids (5–11) were isolated from the whole plants of Ajuga forrestii. Among them, 3α-acetoxy-1α,8β-dihydroxyeudesm-7(11)-en-8,12-olide (1), 3α-acetoxy-1α-hydroxyl-eudesm-8,7(11)-dien-8,12-olide (2), 1α-acetoxy-8α-oxyethyl-2-oxo-eudesman-3,7(11)-dien-8,12-olide (3) and 2α,3β,11,12-tetrahydroxy-7β,20-epoxy-8,11,13-abietatriene (11) are novel compounds. The structures of compounds 1–11 were determined by spectroscopic analysis. Compound 2 exhibited weak cytotoxicity on HepG2 and MCF-7 cell lines.     

Three new triterpenes from the lichen Xanthoria resendei

The three new migrated hopene type triterpenes 12α-acetoxy-3β-hydroxyfern-9(11)-ene, 3β,12α-dihydroxyfern-9(11)-ene and 3,12-diketofern-9(11)-ene have been isolated from the ether extracts of the lichen Xanthoria resendei, together with peroxyergosterol and the anthraquinone pigments physcion, fallacinal and fallacinol.     

Further triterpenoids and 13C NMR spectra of oleanane derivatives from Phytolacca acinosa

In addition to five known triterpenoids, namely acinosolic acid, phytolaccagenin, phytolaccagenic acid, esculentic acid and jaligonic acid, three new oleanane derivatives, designated as phytolaccagenin A, acinosolic acid A and acinosolic acid B, have been isolated and characterized from the defatted berries of Phytolacca acinosa. The new compounds have been identified as 3β-acetoxy-3β-methyloleanate-12-en-2β,23α-diol-28β-oic acid, 3β-acetoxy-28β-methyloleanate-12-en-2β-ol-30β-oic acid and 2β-acetoxy-28β-methyloleanate-12-en-3β-ol-30β-oic acid, respectively.     

The structure of leocardin,two epimers of a diterpenoid from Leonurus cardiaca

From the aerial part of Leonurus cardiaca a new labdane diterpenoid, leocardin, has been isolated and its structure was established by spectroscopic and chemical means. It has been shown to be 8β-acetoxy-9α,13α,15,16-bisepoxy-15-hydroxy-7-oxo-labdan-6β,19-olide present as a C-15 epimeric mixture.     

A neo-clerodane glucoside and neo-clerodane diterpenoids from Teucrium flavum subsp. Glaucum

From the aerial part of Teucrium flavum subsp. glaucum a new neo-clerodane diterpenoid, teuflavin, and a new 19-nor-neo-clerodane glucoside, teuflavoside, have been isolated, besides the previously known diterpene teuflin. The structures of teuflavin (19-acetoxy-4α,18:15,16-diepoxy-6β-hydroxy-3-keto-neo-cleroda-13(16),14-diene-20,ξ,12S-hemiacetal) and teuflavoside (18-acetoxy-15,16-epoxy-19-nor-neo-cleroda-4,13(16),14-trien-20,12S-olid-6β-yl-2′-O-acetyl-β-d-glucopyranoside) were established by chemical and spectroscopic means and by correlation with known compounds. In addition, the previously known flavone salvigenin has also been obtained from the same source.     

Steroid derivatives

Hydroxylation of l7α-acetoxy-6-chloro-16-methylene-4,6-pregnadiene-3,20-dione (Chlorosuperlutin, I) byCunninghamella blakesleeana yielded a 15β-hydroxyderivative II. Analogous transformation of 17α-acetoxy-16-methylene-4,6-pregnadiene-3,20-dione (Superlutin, IV) included a hydroxylation in position 15β and probably also in 11β with a concomitant reduction of the 6,7-double bond.     

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.     

Trichothecene mycotoxins from Fusarium sulphureum

Four mycotoxins isolated from moulded maize cultures of Fusarium sulphureum have been characterized as 3α,4β,15-triacetoxy-12,13-epoxytrichothec-9-ene, 4β,15-diacetoxy-3α-hydroxy-12,13-epoxytrichothec-9-ene, 15-acetoxy-3α,4β-dihydroxy-12,13-epoxytrichothec-9-ene and 4β-acetoxy-3α,15-dihydroxy-12,13-epoxytrichothec-9-ene.     

Teumarin a neo-clerodane diterpenoid from Teucrium marum

A new neo-clerodane diterpenoid, teumarin, was isolated from the aerial part of Teucrium marum. Its structure, 19-acetoxy-4α,18:15,16-diepoxy-2β,6β-dihydroxy-neo-cleroda-13(16),14-dien-20,12S-olide, was established by chemical and spectroscopic means and by comparison with closely related compounds.     

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.     

Three new dihydroagarofuran sesquiterpenoids from Celastrus orbiculatus

Three new β-dihydroagarofuran sesquiterpene polyesters, 1β-acetoxy-8α,9β-dibenzoyloxy-13-nicotinoyloxy-β-dihydroagarofuran (1), 1β,2β-diacetoxy-9α-benzoyloxy-13-nicotinoyloxy-β-dihydroagarofuran (2), and 6α,8α,9β,13-tetraacetoxy-1β-cinnamoyloxy-2β,4α-dihydroxy-β-dihydroagarofuran (3) were isolated from the fruits of Celastrus orbiculatus Thunb. Their structures were determined by means of extensive spectroscopic analyses (IR, ESIMS, HRESIMS, 1D and 2D NMR).     

Neo-clerodane diterpenoids from Teucrium pyrenaicum

From the aerial part of Teucrium pyrenaicum three new neo-clerodane diterpenoids have been isolated. Their structures, 3β-acetoxy-4α,18:12S,2OS: 15,16:19, 2OS-tetraepoxy-neo-cleroda-13(16),14-dien-6-one (teupyrenone), 3β,6α,19-triacetoxy- 4α,18:15,16-diepoxy-neo-cleroda-13(16),14-dien-20,12S-olide (teupyreinin), and 3β, 6α,19,2OS-tetra-acetoxy-4α,18:12S,2OS: 15,16-triepoxy-neo-cleroda-13(16), 14-diene (teupyreinidin), were established mainly by spectroscopic means.