Microbial transformation of dehydroepiandrosterone

Transformation of dehydroepiandrosterone (DHEA) (1) was carried out by a plant pathogen Rhizopus stolonifer, which resulted in the production of seven metabolites. These metabolites were identified as 3beta,17beta-dihydroxyanandrost-5-ene (2), 3beta,17beta-dihydroxyandrost-4ene (3), 17beta-hydroxyandrost-4-ene-3-one (4), 3beta,11-dihydroxyandrost-4-ene-17-one (5), 3beta,7alpha-dihydroandrost-5-ene-17-one (6), 3A,7alpha,17beta-trihydroxyandrost-5-ene (7) and 11beta-hydroxyandrost-4,6-diene-3,17-dione (8). The structures of the transformed products were determined by the spectroscopic techniques.     

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.     

Cycloartane triterpenes from Euphorbia tuckeyana

Investigation of the acetone extract of the whole plant of Euphorbia tuckeyana afforded a new cycloartane-type triterpene named as cyclotucanol. Its structure was established as cycloartane-24-methylene-3beta,25-diol (1). The known cycloartane triterpenes cycloeucalenol (2), 3beta-hydroxycycloart-25-en-24-one (3), cycloart-25-ene-3beta,24-diol (4), 25,26,27-trisnor-3beta-hydroxycycloartan-24-al (5) and cycloart-23-ene-3beta,25-diol (6) were also isolated and identified.     

Six new dammarane-type triterpene saponins from the leaves of Panax ginseng

Six new minor saponins, together with known ginsenosides, were isolated from the leaves of Panax ginseng. The new saponins were named as ginsenoside-Rh5, -Rh6, -Rh7 -Rh8, -Rh9 and -Rg7, and their structures were elucidated on the basis of chemical and physicochemical evidence to be as follows: ginsenoside-Rh5: 3beta,6alpha,12beta,24zeta-tetrahydroxy-dammar-20(22),25-diene 6-O-beta-D-glucopyranoside (1), -Rh6: 3beta,6alpha12beta,20(S)-tetrahydroxy-25-hydroperoxy-dammar-23-ene 20-O-beta-D-glucopyranoside (2), -Rh7: 3beta,7beta,12beta,20(S)-tetrahydroxy-dammar-5,24-diene 20-O-beta-D-glucopyranoside (3), -Rh8: 3beta,6alpha,20(S)-trihydroxy-dammar-24-ene-12-one 20-O-beta-D-glucopyranoside (4), -Rh9: 3beta,6alpha,20(S)-trihydroxy-12beta,23-epoxy-dammar-24-ene 20-O-beta-D-glucopyranoside (5) and -Rg7: 3-O-beta-D-glucopyranosyl 3beta,12beta,20(S),24(R)-tetrahydroxy-dammar-25-ene 20-O-beta-D-glucopyranoside (6).     

Compositions of royal jelly II. Organic acid glycosides and sterols of the royal jelly of honeybees (Apis mellifera)

Two organic acid glycosides (1, 2) and 16 sterols were isolated from the royal jelly of honeybees (Apis mellifera). The former two were monoglucosides of 10-hydroxy-2E-decenoic and 10-hydroxydecanoic acids. They are the first examples of glycosides isolated from royal jelly. The latter 16 were sterols mainly composed of 28 or 29 carbons. Among them, four compounds were new isofucosterol derivatives, and their structures were characterized as (24Z)-stigmasta-5,24(28)-dien-3beta-ol-7-one (3), (24Z)-stigmasta-5,24(28)-diene-3beta,7beta-diol (4), (24Z)-stigmasta-5,24(28)-diene-3beta,7alpha-diol (5), and (24Z)-stigmast-24(28)-ene-3beta,5alpha,6beta-triol (6) on the basis of various NMR spectroscopic data.     

Microbial hydroxylation of pregnenolone derivatives

Pregnenolone and pregnenolone acetate were incubated with the fungi Cunninghamella elegans, Rhizopus stolonifer and Gibberella fujikuroi. Incubation of with C. elegans yielded metabolites, 3beta,7beta,11alpha-trihydroxypreg-5-en-20-one, 3beta,6alpha,11alpha,12beta,15beta-pentahydroxypreg-4-en-20-one and 3beta,6beta,11alpha-trihydroxypreg-4-en-20-one, while incubation with G. fujikuroi yielded two known metabolites, 3beta,7beta-dihydroxypregn-5-en-20-one and 6beta,15beta-dihydroxypreg-4-ene-3,20-dione. Metabolites and were found to be new. Fermentation of by C. elegans yielded four known oxidative metabolites, androsta-1,4-diene-3,17-dione, 6beta,15beta-dihydroxyandrost-4-ene-3,17-dione and 11alpha,15beta-dihydroxypreg-4-ene-3,20-dione. Fermentation of with R. stolonifer yielded two known metabolites, 11alpha-hydroxypreg-4-ene-3,20-dione and. Compounds were screened for their cholinesterase inhibitory activity in a mechanism-based assay.     

A new cerebroside from fruits of Ailanthus altissima Swingle

A new cerebroside and three known cycloartan triterpenes were isolated from fruits of Ailanthus altissima Swingle. Their structures were identified as 1-O-beta-D-glucopyranosyl-(2S, 3R, 4E, 9E)-2-(2'R-hydroxyhexadecenoy)-4, 9-octadecadiene-1, 3-diol (1), 9, 19-cyclolanost-23 (Z)-ene-3beta, 25-diol (2), cycloart-25-ene-3beta, 24R-diol (3), and cycloart-25-ene-3beta, 24S-diol (4) by means of chemical and spectroscopic analysis. Compounds 2, 3, and 4 were isolated from genus Ailanthus for the first time. The analgesic activity of 1 was also evaluated.     

Unusual sulfated marine steroids from the ophiuroid ophioderma longicaudum

Polar extracts of the ophiuroid Ophioderma longicaudun contain unusual sterol sulfates together with a mixture of common 3β-hydroxysterol sulfates. The more polar compound has been shown to be 5β-cholestane-3, 4,11β,12β,21-pentol 3,21-disulfate 1. A second group of unusual compounds are disulfated 3,21-dihydroxysteroids. After solvolysis to remove the sulfate groups they have been identified as : (20R)-5-cholestane-3, 21-diol 4a, (20R)-cholest-5-ene-3,21-diol 5a, (20R22E)-cholest-5,22-diene-3,21-diol 6a and (20R)-24-methylcholest-5,24(28)-diene-3,21-diol 7a. Analysis of the “non-sulfated” sterol fractions has shown the presence of common 3β-hydroxy sterols.     

Five new sesquiterpenoids and a new diterpenoid from Erigeron annuus (L.) PERS., Erigeron philadelphicus L. and Erigeron sumatrensis RETZ

The aerial parts of Erigeron annuus (L.) PERS., E. philadelphicus L. and E. sumatrensis RETZ. (Compositae) have been investigated chemically. A new sesquiterpenoid, 6beta,14-epoxyeudesm-4(15)-en-1beta-ol (1), and a new diterpenoid, philadelphinone (6), have been isolated from E. philadelphicus. Four new sesquiterpenoids, (7R*)-opposit-4(15)-ene-1beta,7-diol (2), 11-methoxyopposit-4(15)-en-1beta-ol (3), 15-methoxyisodauc-3-ene-1beta,5alpha-diol (4) and 10alpha-hydroxycadin-4-en-15-al (5), have been isolated from E. annuus. Compounds 2 and 4 were also isolated from E. sumatrensis. The structures of the new compounds were elucidated on the basis of their spectral data.     

Synthesis of 16 alpha-hydroxyandrost-4-ene-3,17,19-trione and 3 beta, 16 alpha-dihydroxyandrost-5-ene-17,19-dione; potential intermediates of estriol biosynthesis

16 alpha-Hydroxyandrost-4-ene-3,17,19-trione (10) was synthesized from the 16 alpha-hydroxy-6 beta,19-epoxy-17-one 3 via protection of the 16 alpha-hydroxy function as its tert-butyldimethylsilyl ether or acetate. Reductive cleavage of the epoxy ring of the silyl ether 4 or the acetate 5 with zinc dust gave the 19-alcohol 6 or 7, which was treated with pyridinium dichromate or Jones reagent, respectively, and then hydrolyzed with diluted sulfuric acid, yielding the desired steroid 10. 3 beta,16 alpha-Dihydroxyandrost-5-ene-17,19-dione (14) was also synthesized from 5 alpha-bromo-3 beta,16 alpha-diacetoxy-6 beta, 19-epoxyandrostan-17-one (11) through the intermediates 12 and 13 with the 3 beta- and 16 alpha-hydroxy functions protected as their acetates in a reaction sequence similar to that above.     

Synthesis of deuterium-labeled 16 alpha,19-dihydroxy C19 steroids as internal standards for gas chromatography-mass spectrometry.

[2 beta,7,7,16 beta-2H4]16 alpha,19-Dihydroxyandrost-4-ene-3,17-dione (14) and [7,7,16 beta-2H3]3 beta,16 alpha,19-trihydroxyandrost-5-en-17-one (16), with high isotopic purity, respectively, were synthesized from unlabeled 3 beta-(tert-butyldimethylsiloxy)-androst-5-ene-17 beta-yl acetate (1). The deuterium introduction at C-7 was carried out by reductive deoxygenation of the 7-keto compound 3 with dichloroaluminum deuteride and that at C-2 beta and/or C-16 beta by controlled alkaline hydrolysis of 16-bromo-17-ketone 11 or 12 with NaOD in D2O and pyridine. [7,7-2H2]3 beta-Hydroxyandrost-5-en-17-one (6), obtained from compound 1 by a five-step sequence, was converted to compound 14 or 16 by an eight-step or seven-step sequence, respectively. The labeled steroids 14 and 16 are useful as internal standards for gas chromatography-mass spectrometry analysis of the endogenous levels.     

Cytotoxic sterols from marine-derived fungus Pennicillium sp

A new sterol, ergosta-8(14), 22-diene-3,5,6,7-tetraol(3beta, 5alpha, 6beta, 7alpha, 22E) (1), together with four known sterols ergosta-8(9), 22-diene-3,5,6,7-tetraol (3beta, 5alpha, 6beta, 7alpha, 22E) (2), 5alpha,8alpha-epidioxy-24(S)-methylcholesta-6,22-diene-3beta-ol (3), 5alpha,8alpha-epidioxy-24(S)-methylcholesta-6,9(11), 22-triene-3beta-ol (4), 3beta,5alpha,9alpha-trihydroxyergosta-7,22-diene-6-one (5) was isolated from marine fungus Pennicillium sp. Their structures were determined based on chemical analysis and spectral methods (IR, 1D and 2D NMR, HR-FAB-MS). Compounds 1-5 were evaluated for cytotoxicity against human liver cancer cell (Hep G), and most of them exhibited potent activity. Compound 1 display the highest potency with IC50 values 10.4 microg mL-1.     

Cadinane-type sesquiterpenes from the roots of Taiwania cryptomerioides Hayata

Five new cadinane-type sesquiterpenes, 15-acetoxy-T-muurolol (1), isokhusinodiol (2), cadin-10(14)-ene-4beta,5alpha-diol (3), cadinane-4beta,5alpha,10beta-triol (4), and muurolane-4beta,5beta,10beta-triol (5), together with five known compounds, T-cadinol (6), T-muurolol (7), alpha-cadinol (8), delta-cadinol (9), and khusinodiol (10), were isolated from the roots of Taiwania cryptomerioides. The structure of the new constituents were elucidated through chemical and spectral studies.     

Steroid compounds from ophiuroids II. Sulfated steroids from Ophiura sarsi and Ophiura leptoctenia

The previously described cholest-5-ene-3,4,21-triol 3-(sodium sulfate) has been obtained from extracts of the Far Eastern ophiuroidOphiura leptoctenia. Two new sulfated steroid polyols have been isolated from the ophiuroidO.sarsi; cholest-5-ene-3,4,21-triol 3,21-di(sodium sulfate) and cholest-5-ene-2,3,21-triol tri(sodium sulfate). The new polyol 4-acetoxycholest-5-ene-3,21-diol has been identified among the products of the desulfation of this ophiuroid.Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Branch, Academy of Sciences of the USSR, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 483–487, July–August, 1990.     

Synthesis of 24-Methylidene[24-14C]- and 24-Methylidene[7-3H]cholesterol

The syntheses of 24-methylidene[24-¹⁴C]cholesterol ( 7a ) and of 24-methylidene[7-³H]cholesterol ( 7b ) from commercially available (20S)-3-oxopregn-4-ene-20-carbaldehyde ( 1 ) are described. The method also provides simple preparations of 3β-acetoxy[24-¹⁴C]chol-5-en-24-oic acid ( 4 ) and 24-oxocholest-5-en-3β-yl acetate ( 6b ).     

三个新甾体皂甙元的结构鉴定

从中药蒺藜Tribulus terrestrisL.(Zygophyllaceae）中分离纯化得到5个 甾体皂甙元，经IR，2D-NMR和MS等波谱技术分别鉴定为：海可皂甙元(1)，25(R)-螺 甾烷-4—烯—3，12—酮(2)，25(R)·螺甾烷—3，5-二烯—12—酮(3)，25(R)-螺 甾烷-4—烯—2β，3α-二羟基—12—酮(4)和25(R)—螺甾烷—24β—羟基-4—烯 —3，12—酮(5)，其中化合物3-5为新化合物．     

A new cytotoxic cholesterol sulfate from marine sponge Halichondria rugosa

A new steroid, 24xi,25-dimethyl-3alpha-hydroxyl-cholest-5-ene-2beta-ol sodium sulfate (1), together with a known steroid, 24xi,25-dimethyl-cholest-5-ene-2beta,3alpha-diol disodium sulfate (2), was isolated from the ethanol extract of marine sponge Halichondria rugosa. Their structures were elucidated on the base of spectroscopic analysis. Both compounds showed cytotoxicity to four human cancer cell lines (BEL-7402, HT-29, SPC-A1 and U-251) with IC(50) values between 6.5 and 23.1 microM.     

Medicinal foodstuffs. XVII. Fenugreek seed. (3): structures of new furostanol-type steroid saponins, trigoneosides Xa, Xb, XIb, XIIa, XIIb, and XIIIa, from the seeds of Egyptian Trigonellafoenum-graecum L

Six new furostanol-type steroid saponins called trigoneosides Xa, Xb, XIb, XIIa, XIIb, and XIIIa were isolated from the seeds of Egyptian Trigonella foenum-graecum L. (Leguminosae) together with six known furostanol-type steroid saponins: trigoneosides Ia, Ib, and Va, glycoside D, trigonelloside C, and compound C. The structures of trigoneosides Xa, Xb, Xlb, XIIa, Xllb, and XIIIa were determined on the basis of chemical and physicochemical evidence as 26-O-beta-D-glucopyranosyl-(25S)-5alpha-furostane-2alpha+ ++,3beta,22xi,26-tetraol 3-O-alpha-L-rhamnopyranosyl(1-->2)-,beta-D-glucopyranoside, 26-O-beta-D-glucopyranosyl-(25R)-5alpha-furostane-2 alpha,beta,22xi,26tetraol 3-O-alpha-L-rhamnopyranosyl(l -->2)-beta-D-glucopyranoside, 26-O-beta-D-glucopyranosyl-(25R)-5alpha-furostane2alpha++ +,beta,22xi,26-tetraol 3-O-beta-D-xylopyranosyl(l -->4)-beta-D-glucopyranoside, 26-O-beta-D-glucopyranosyl-(25S)-furost-4-ene-3beta,22xi,26- triol 3-O-Ca-L-rhamnopyranosyl(1-->2)-beta-D-glucopyranoside, 26-O-beta-D-glucopyranosyl-(25R)-furost-4-ene-3beta,22xi+ ++,26-triol 3-O-alpha-L-rhamnopyranosyl(1-->2)-beta-D-glucopyranoside, and 26-O-beta-D-glucopyranosyl(25S)-furost-5-ene-3beta,22xi,26-t riol 3-O-alpha-L-rhamnopyranosyl(1-->2)-beta-D-glucopyranosyl (1-->3)-beta-D-glucopyranosyl(1--4)]-beta-D-glucopyranoside, respectively.     

Complete assignments of 1H and 13C NMR spectral data for three new triterpenoid saponins from Ilex hainanensis Merr

Three new oleanane-type triterpenoid saponins, ilexhainanoside C, D and E, all with 24, 28-dioic acid groups, were isolated from the leaves of Ilex hainanensis. They were 3beta-hydroxyolean-12-ene-24, 28-dioic acid-28-O-beta-D-glucopyranoside(1), 3beta, 19alpha-dihydroxyolean-12-ene-24, 28-dioic acid-28-O-beta-D-glucopyranoside(2) and 3beta, 29-dihydroxyolean-12-ene-24, 28-dioic acid-28-O-beta-D-glucopyranoside(3). The structures of these three new compounds were elucidated and complete assignments of the (1)H and (13)C NMR spectroscopic data were achieved by 1D and 2D NMR experiments [heteronuclear single quantum coherence (HSQC), HMBC and rotational nuclear Overhauser effect spectroscopy (ROESY)].     

Pregnane glycosides, gymnepregosides G-Q from the roots of Gymnema alternifolium.

The structural elucidation of eleven new related polyoxypregnane glycosides, gymnepregosides G (1), H (2), I (3), J (4), K (5), L (6), M (7), N (8), O (9), P (10) and Q (11), from the roots of Gymnema alternifolium (Asclepiadaceae) was achieved by a detailed study of 1H- and 13C-NMR spectral data and chemical means. The results obtained for new compounds, 1-11, show that they are (20S)-pregn-6-ene-3 beta,5 alpha,8 beta,12 beta,14 beta,17 beta,20-heptaol 3-O-glycosides, and all the sugars at C-3 are beta(i-->4)-linked. Some of them possess benzoyl, (E)- and (Z)-cin-namoyl, and tigloyl residues as the ester linkages located at C-12 and/or C-20 of the aglycone.