Steroidal constituents of Solanum xanthocarpum

From the extract of the fruits of Solanum xanthocarpum (Solanaceae), five new steroidal compounds were isolated and characterized: 4α-methyl-24ξ-ethyl-5α-cholest-7-en-3β,22ξ-diol (1), 3β,22ξ-dihydroxy-4α-methyl-24ξ-ethyl-5α-cholest-7-en-6-one (2), 3β-benzoxy-14β,22ξ-dihydroxy-4α-methyl-24ξ-ethyl-5α-cholest-7-en-6-one (3), 3β-benzoxy-14α,22ξ-dihydroxy-4α-methyl-24ξ-ethyl-5α-cholest-7-en-6-one (4) and 3β-(p-hydroxy)-benzoxy-22ξ-hydroxy-4α-methyl-24ξ-ethyl-5α-cholest-7-en-6-one (5).     

Sterols with unusual nuclear unsaturation from three cultured marine dinoflagellates

Several new 4α-methyl sterols with unusual unsaturation in the Δ⁸⁽¹⁴⁾-or Δ¹⁴-positions, 4α,24S-dimethyl-5α-cholest-8 (14)-en-3β-ol, 4α-methyl-24ξ-ethyl-5α-cholest-8(14)-en-3β-ol, 4α-methyl-24(Z)-ethylidene-5α-cholest-8(14)- en-3β-ol, 4α,23 (or 22),24ξ-trimethyl-5α-cholesta-8(14),22-dien-3β-ol, 4α,24S(or 23ξ)-dimethyl-5α-cholest-14-en-3β-ol and 14-dehydrodinosterol, have been isolated from extracts of the cultured marine dinoflagellates Amphidinium carterae, A. corpulentum and Glenodinium sp. 4α-Methyl-24ξ-ethyl-5α-cholestan-3β-ol was isolated from the steryl ester fraction of Glenodinium sp. The structures of these new sterols are based upon extensive 360 MHz ¹H NMR and MS analyses.     

Dinoflagellate sterols IV: Isolation and structure of 4α,23ξ,24ξ-trimethylcholestanol from the dinoflagellate Glenodiniumhallii

The dinoflagellate $\text{Glenodinium}$$\text{hallii}$ was investigated for its sterol composition. Five of the six sterols were isolated and identified as cholest-5-en-3β-ol, (24ξ)-24-methylcholest-5-en-3β-ol, stigmasta-5,22-dien-3β-ol, (22E,24R)-4α,23,24-trimethyl-5α-cholest-22-en-3β-ol, and 4α,23ξ,24ξ-trimethyl-5α-cholestan-3β-ol.     

Beesioside III,a cyclolanostanol xyloside from the rhizomes of Beesia calthaefolia and Souliea vaginata

The chemical constituents of Beesia calthaefolia and Souliea vaginata were examined. From the rhizomes of B. calthaefolia, four new 9,19-cyclolanostanol xylosides, named beesiosides I–IV were isolated. Beesiosides 111 and IV were found also in the rhizomes of S. vaginata. On the basis of chemical and spectral evidence the structure of beesioside III was established as 15α-acetoxy-20ξ₁,24ξ₂-epoxy-9,19-cyclolanostane-3β,12β,16β,25-tetraol-3-O-β-D-xylopyranoside.     

A furostanol glucuronide from Solanum lyratum

A new furostanol glucuronide and three known glycosides, SL-O, aspidistrin and methyl proto-aspidistrin, were isolated from the fresh immature berries of Solanum lyratum. The structure of the new compound was characterized as 26-O-β-D-glucopyranosyl-(22ξ,25R-3β,22,26-trihydroxyfurost-5-ene 3-O-α-L-rhamnopyranosyl-(1 → 2)-[β-D-glucopyranosyl-(1 → 3)]-β-D-glucuronopyranoside.     

Minor sterols of marine invertebrates 37. Isolation of novel coprostanols and 4α-methyl sterols from the tunicate Ascidia nigra

The complex sterol mixture isolated from $\text{A, nigra}$ was found to contain a low level of Δ⁴-3-keto steroids, 5β-stanols and 4α-methyl sterols in addition to regular (4-demethyl) sterols. The following new marine sterols were isolated and identified using MS and 360 MHz NMR: 5β-cholest-22E-en-3β-ol, 24S-methyl-5β-cholest-22E-en-3β-ol, 24-methylene-5β-cholestan-3β-ol, both epimers at C-24 of 4α-methyl-24-ethyl-5α-cholest-22E-en-3β-ol, 4α, 22ξ, 23ξ-(or 24ξ-)trimethyl-5α-cholest-8(14)-en-3β-ol and (22S, 23S, 24S)-4α-24-dimethyl-22, 23-methylene-5α-cholestan-3β-ol. The latter sterol and 23-demethylgorqosterol have opposite configurations at C-22, C-23, and C-24; the Δ⁸⁽¹⁴⁾ sterol has an unprecedented side chain.     

Novel dinoflagellate 4α-methylated sterols from four caribbean gorgonians

Fourteen 4α-methyl sterols have been isolated from the gorgonians Briareum asbestinum, Gorgonia mariae, Muriceopsis flavida and Pseudoplexaura wagenaari, including the following five new sterols: 4α-methyl-24-methylene-5α-cholestan-3β-ol, (24R)-4α, 24-dimethyl-5α-cholesta-7,22-dien-3,β-ol, 4α,24S(or 23ξ)-dimethyl-5α-cholest-7-en-3β-ol, (22E, 24R)-4α,23,24-trimethyl-5α-cholesta-7,22-dien-3β-ol and (24R)-4α,24-dimethyl-5α-cholesta-8(14),22-dien-3β-ol. There is strong evidence that these 4α-methyl sterols are synthesized by the algal (dinoflagellate) symbionts (zooxanthellae) of the gorgonians. It is suggested that analysis of 4Δ-methyl sterol mixtures isolated from a zooxanthellae-bearing invertebrate, collected in several different geographic locations, might give information on the specificity of the symbiotic association between a given animal species and a particular strain of zooxanthellae.     

旋花茄新鲜果实中的三个甾体皂苷

从茄科食用植物旋花茄(Solanum spirde)的新鲜果实中分离得到3个化合物,其中一个为新成分,经现代波谱学方法鉴定为26-0-β-D-葡萄吡喃糖基-(25R)-呋甾-3β,22ξ,26-三醇-5-烯-3-0-α-L-鼠李吡喃糖基-(1-2)-[3-0-(3-O-乙酰基)-α-L-鼠李吡喃糖基-(1-4)]-β-D-葡萄吡喃糖苷(1).2个已知化合物分别为26-O-β-D-葡萄吡喃糖基-(25R)-呋甾-22ξ-甲氧基-3β,26-二醇-5-烯-3-O-α-L-鼠李吡哺糖基-(1-2)-β-D-葡萄吡喃糖苷(2)和26-O-β-D-葡萄吡喃糖基-(25R)-呋甾-3β,22ξ,26-三醇-5-烯-3-O-α-L-鼠李吡喃糖基-(1-2)-[α-L-鼠李吡喃糖基-(1-4)]-β-D-葡萄吡喃糖苷(protodioscin)(3),均为首次从该植物中分离得到.     

Co-occurrence of °5- and °7-sterols in two gleditsia species. : A reassessment of the sterol composition in oils rich in °7 -sterols

The composition of the sterol fraction of Gleditsia triacanthos, G. macracantha, Thea sinensis, Medicago sativa and Spinacia oleracea has been determined using GC and GC/MS. The sum of δ⁷-sterols ranges from 67 to 95%. Among them 24ξ-ethyl-5α-cholest-7,trans-22-dien-3β-ol (28–50%) and 24ξ-ethyl-5α-cholest-7-en-3β-ol (23–49%) are the major components. The co-occurrence of δ⁵- and δ⁷-sterols has been observed in all species. The possible biosynthetic pathway of the phytosterol nucleus leading to these sterols is discussed.     

Configuration at C-24 of sterols from the liverwort Palavicinnia lyellii

The 4-desmethylsterol fraction of the liverwort Palavicinnia lyellii is composed of 36% 24β-methylcholest-5-en-3β-ol (dihydrobrassicasterol), 16% 24α-methylcholest-5-en-3β-ol (campesterol), 33% 24α-ethylcholest-5-en-3β-ol (sitosterol) and 15% 24ξ-ethylcholesta-5,22-dien-3β-ol.     

Proton magnetic resonance spectra of 17ξ-Hydroxy-17ξ-methyl-5ξ-androstane C-3 ketone and c-3ξ alcohol isomers in chloroform-d and pyridine-d5

17α-Hydroxy-17β-methyl-5β-androstan-3-one, 17μ-methyl-5α-androstane-3α, 17α-diol, 17β-methyl-5α-androstane-3β, 17α-diol, 17α-methyl-5β-androstane-3β, 17β-diol, 17β-methyl-5β-androstane-3α, 17α-diol and 17β-methy1–5β-androstane-3β, 17α-diol were synthesized for the first time. ¹H NMR spectra of all four 17ξ-hydroxy/17ξ-methyl C-3 ketones and all eight C-3 alcohols were recorded in chloroform-d and pyridine-d₅. Pyridine-induced chemical shifts are discussed. Thin-layer Chromatographic data are given.     

Acyl migration in the Reformatsky reaction of 21-acyloxy-5-pregnen-20-one derivatives with ethyl bromoacetate

Reformatsky reaction of 3β, 21-diacyloxy- and 3β-methoxy-21-acyloxy-5-pregnen-20-one with ethyl bromoacetate yields, through an intramolecular 1,2-acyl migration, 3β, 20ξ-diacyloxy- and 3β-methoxy-20ξ-acyloxy-14α-card-5-enolide respectively. The 20ξ-acyloxy-14α-card-5-enolides were converted into the respective 20ξ-hydroxy-14α-card-5-enolides and the 14α-carda-5,20(22)-dienolides. Experimental support to the proposed intramolecular 1,2-acyl migration is provided by the use of labelled compounds.     

Chemical synthesis of the 17-propanamide derivatives of stereoisomeric Δ14-17α- and 17β-estradiols: potential 17β-hydroxysteroid dehydrogenase inhibitors

The 17-propanamide derivatives of diastereomeric Δ¹⁴-17α- and 17β-estradiols, the potential candidates of a 17β-hydroxysteroid dehydrogenase (17β-HSD) inhibitor, were synthesized in 11 steps from estrone. The principal reactions employed involved in (1) conversion of estrone to the corresponding Δ¹⁴-estrone, (2) Grignard reaction of Δ¹⁴-estrone with allylmagnesium bromide followed by regioselective hydroboration of the resulting stereoisomeric 17ξ-allyl-Δ¹⁴-17ξ-ols with 9-borabicyclo[3.3.1]nonane (9-BBN), and (3) direct amidation of the 17ξ-O-/17ξ-C-spiro-γ-lactones with NH₃ under positive pressure of H₂.     

Neo-clerodane diterpenoids from Teucrium pyrenaicum and T. subspinosum

From the aerial parts of teucrium pyrenaicum two new neo-clerodane diterpenoids, teupyrins A and B, have been isolated. The structures of teupyrin A [3β,12S-diacetoxy-4α,18; 15,16-diepoxy-6-keto-neo-cleroda-13(16),14-diene-20R,19-hemiacetal] and teupyrin B [6α-acetoxy-4α,18; 15,16-diepoxy-3β,12ξ,19-trihydroxy-neo-cleroda-13(16),14-diene] were established mainly by spectroscopic means and, in the case of teupyrin A, by X-ray diffraction analysis. The acetone extract of the aerial parts of T. subspinosum yielded four previously known neo-clerodane diterpenoids: teucvin, teuflin, teucrin H2 and 6α-hydroxyteuscordin.     

Detection of designer steroid methylstenbolone in “nutritional supplement” using gas chromatography and tandem mass spectrometry: Elucidation of its urinary metabolites

The use of “nutritional supplements” containing unapproved substances has become a regular practice in amateur and professional athletes. This represents a dangerous habit for their health once no data about toxicological or pharmacological effects of these supplements are available. Most of them are freely commercialized online and any person can buy them without medical surveillance. Usually, the steroids intentionally added to the “nutritional supplements” are testosterone analogues with some structural modifications.In this study, the analyzed product was bought online and a new anabolic steroid known as methylstenbolone (2,17α-dimethyl-17β-hydroxy-5α-androst-1-en-3-one) was detected, as described on label. Generally, anabolic steroids are extensively metabolized, thus in-depth knowledge of their metabolism is mandatory for doping control purposes. For this reason, a human excretion study was carried out with four volunteers after a single oral dose to determine the urinary metabolites of the steroid. Urine samples were submitted to enzymatic hydrolysis of glucuconjugated metabolites followed by liquid–liquid extraction and analysis of the trimethylsilyl derivatives by gas chromatography coupled to tandem mass spectrometry. Mass spectrometric data allowed the proposal of two plausible metabolites: 2,17α-dimethyl-16ξ,17β-dihydroxy-5α-androst-1-en-3-one (S1), 2,17α-dimethyl-3α,16ξ,17β-trihydroxy-5α-androst-1-ene (S2). Their electron impact mass spectra are compatible with 16-hydroxylated steroids O-TMS derivatives presenting diagnostic ions such as m/z 231 and m/z 218. These metabolites were detectable after one week post administration while unchanged methylstenbolone was only detectable in a brief period of 45 h.     

苋科植物的丛枝菌根

有些种子植物如莎草科、十字花科、灯心草科、藜科、石竹科等20余科,以往曾被认为不能或不易形成丛枝菌根(郭秀珍等,1989;刘润进等,2000).随着对菌根的深入研究,曾被认为是不易与菌根菌组合的湿地生植物、寄生性植物、或一年生植物都被发现是可以形成内生菌根的(Trappe等,1992).此外,Allen等(1989)研究证实,Salsola kali,Atriplex roseum等生长于沙漠、海滨的藜科植物,进行接种处理后,也能形成丛枝菌根.我们在西双版纳调查热带雨林植物的丛枝菌根状况时,偶然发现刺苋(Amaranthus spinosus Linn.)的根系受到了丛枝菌根真菌的侵染,因此,对苋科植物作了扩大采样调查.本文主要报道从热带采集的5属6种苋科植物的根受丛枝菌根真菌感染形成丛枝菌根(arbuscular mycorrhiza,AM)和这些植物根际士壤中的丛枝菌根真菌(arbuscular mycorrhizal fungi,AMF)的状况.     

Biosynthesis of the butenolide ring of cardenolides in Digitalis purpurea

Administration of labelled 3β,20ξ-dihydroxy-23-norchol-5-enoic acid, 3-oxo-20ξ-hydroxy-23-norchol-4-enoic acid, 3β,20ξ-dihydroxy-23-nor-5β-cholanoic acid, 3β,14β,20ξ-trihydroxy-23-nor-5β-cholanoic acid, 3β-hydroxy-23-norchola-5,20(22)E-dienoic acid, 3-oxo-23-norchola-4,20(22)E-dienoic acid and 3β-hydroxy-23-nor-5β-chol-20(22)E-enoic acid to Digitalis purpurea intact plants produced labelled digitoxin and gitoxin. The incorporation results indicate the existence of an alternative pathway, via norcholanoic acid derivatives, for the biosynthesis of the butenolide ring of cardenolides.     

Polyhydroxylated steroids from an endophytic fungus, Chaetomium globosum ZY-22 isolated from Ginkgo biloba

A novel polyhydroxylated C₂₉-sterol, 25ξ-methyl-22-homo-5α-cholest-7,22-diene-3β,6β,9α-triol, designated globosterol (1), together with one known tetrahydroxylated ergosterol (22E, 24R)-ergosta-7,22-diene-3β,5α,6β,9α-tetraol (2) has been isolated from the cultures of an endophytic fungus, Chaetomium globosum ZY-22 originated from the plant Ginkgo biloba. The structures and relative configurations of 1 and 2 were established on the basis of extensive spectroscopic analyses including 1D and 2D NMR (¹H-¹H COSY, HSQC, HMBC, and NOESY) experiments and comparison with the literature. Globosterol (1) possesses an unprecedented 25-methyl Δ²²-C₁₀-side chain and Δ⁷-3β,6β,9α-hydroxy-steroid nucleus, which represents the first example for C₂₉-steroids of the group.     

Dominance of Δ5-sterols in eight species of the cactaceae

The sterols from eight species in seven genera of the Cactaceae are 24-alkyl-Δ⁵-sterols. In all eight species, Echinopsis tubiflora, Pereskia aculeata, Hylocereus undatus, Notocactus scopa, Epiphyllum sp., Schlumbergera bridgesii, Opuntia comonduensis and O. humifusa, the dominant sterol is sitosterol (24α-ethylcholest-5-en-3β-ol) at 66–87% of the total sterol composition with the 24ξ-methylcholest-5-en-3β-ol present at 8–33%. Stigmasterol (24α-ethylcholesta-5,22E-dien-3β-ol) is present at 2–8% of the total sterol in P. aculeata, H. undatus, N. scopa and Epiphyllum sp. whereas cholesterol (cholest-5-en-3β-ol) is present in six species at levels of <0.1–5.0%. Avenasterol (24-ethylcholesta-7,24(28)Z-dien-3/gb-ol) and sitostanol (24α-ethyl-5α-cholestan-3β-ol) are each present in two species.     

Synthesis of biological precursors of cholic acid

This paper describes a new and convenient procedure for the synthesis of 5β-cholestane-3α,7α,12α,24-tetrol(24R and 24 S) and 5β-cholestane-3α, 7α, 12α, 26-tetrol starting from 5β-cholestane-3α,7α,12α,25-tetrol. Dehydration of the 25-hydroxytetrol with glacial acetic acid and acetic anhydride yielded a mixture of 5β-cholest-24-ene-3α,7α,12α-triol and the corresponding Δ²⁵ compound. Hydroboration and oxidation of the mixture of Δ²⁴ and Δ²⁵ unsaturated bile alcohols resulted in the formation of 5β-cholestane-3α,7α,12α,24ξ-tetrol and 5β-cholestane-3α,7α,12α,26-tetrol. In addition, smaller amounts of 5β-cholestane-3α, 7α, 12α, 23ξ-tetrol and 5β-cholestane-3α, 7α, 12α-triol were also obtained.The bile alcohols epimeric at C-24 were resolved by analytical and preparative TLC, characterized by gas-liquid chromatography and mass-spectrometry. Tentative assignments of the 24R and 24S configuration was made on the basis of molecular rotation differences. These compounds will be useful for biological studies of cholic acid biosynthesis.