20, 21-Azirdin-Steroide: Reaktion von Derivaten der Oxime von 5-Pregnen-20-on,9β,10α-5-Pregnen-20-on und 9β,10α-5,7-Pregnadien-20-on mit Lithiumaluminiumhydrid und von 3β-Hydroxy-5-pregnen-20-on-oxim mit Grignard-Verbindungen

20, 21-Aziridine Steroids: Reaction of Derivatives of the Oximes of 5-Pregnen-20-one, 9β, 10α-5-Pregnen-20-one and 9β, 10α-5,7-Pregnadiene-20-one with Lithium Aluminium Hydride, and of 3β-Hydroxy-5-pregnen-20-one Oxime with Grignard Reagents. Reduction of 3β-hydroxy-5-pregnen-20-one oxime ( 2 ) with LiAlH₄ in tetrahydrofuran yielded 20α-amino-5-pregnen-3β-ol ( 1 ), 20β-amino-5-pregnen-3β-ol ( 3 ), 20β, 21-imino-5-pregnen-3β-ol ( 6 ) and 20β, 21-imino-5-pregnen-3β-ol ( 9 ). The aziridines 6 and 9 were separated via the acetyl derivatives 7 and 10 . The reaction of 6 and 9 with CS₂ gave 5-(3β-hydroxy-5-androsten-17β-yl)-thiazolidine-2-thione ( 8 ). Treatment of the 20-oximes 12 and 15 of the corresponding 9β,10α(retro)-pregnane derivatives with LiAlH₄ gave the aziridines 13 and 16 , respectively. Their deamination led to the diene 14 and triene 17 , respectively. Reduction of isobutyl methyl ketone-oxime with LiAlH₄ in tetrahydrofuran yielded 2-amino-4-methyl-pentane ( 19 ) as main product, 1, 2-imino-4-methyl-pentane ( 22 ) as second product and the epimeric 2,3-imino-4-methyl-pentanes 20 and 21 as minor products. – 3β-Hydroxy-5-pregnen-20-one oxime ( 2 ) was transformed by methylmagnesium iodide in toluene to 20α, 21-imino-20-methyl-5-pregnen-3β-ol ( 23 ) and 20β, 21-imino-20-methyl-5-pregnen-3β-ol ( 26 ). Acetylation of these aziridines was accompanied by elimination reactions leading to 3β-acetoxy-20-methylidene-21-N-acetylamino-5-pregnene ( 30 ) and 3β-acetoxy-20-methyl-21-N-acetylamino-5,17-pregnadiene ( 32 ). The reaction of oxime 2 with ethylmagnesium bromide in toluene gave 20α, 21-imino-20-ethyl-5-pregnen-3β-ol ( 24 ) and 20α,21-imino-20-ethyl-5-pregnen-3β-ol ( 27 ). Acetylation of 24 and 27 led to 3β-acetoxy-20-ethylidene-21-N-acetylamino-5-pregnene ( 31 ), 3β-acetoxy-20-ethyl-21-N-acetylamino-5,17-pregnadiene 33 and 3β, 20-diacetoxy-20-ethyl-21-N-acetylamino-5-pregnene ( 37 ). With phenylmagnesium bromide in toluene the oxime 2 was transformed to 20β, 21-imino-20-phenyl-5-pregnen-3β-ol ( 25 ) and 20β,21-imino-20-phenyl-5-pregnen-3β-ol ( 28 ). Acetylation of 25 and 28 yielded 3β-acetoxy-20-phenyl-21-N-acetylamino-5, 17-pregnadiene ( 34 ) and 3β,20-diacetoxy-20-phenyl-21-N-acetylamino-5-pregnene ( 39 ). LiAlH₄-reduction of 39 gave 3β, 20-dihydroxy-20-phenyl-21-N-ethylamino-5-pregnene ( 41 ). – The 20, 21-aziridines are stable to LiAlH₄. Consequently they are no intermediates in the formation of the 20-amino derivatives obtained from the oxime 2 .     

Synthese eines homologen steroidischen 17β-Pyrrolinons Partialsynthetische Versuche in der Reihe der Herzgifte, 9. Mitteilung

Synthesis of a homologous steroidal 17β-pyrrolinone. We describe the synthesis of 4′-[(3β-Hydroxy-androst-5-en-17β-yl)methyl]-3′-pyrrolin-2′-one ( 15 ) starting from 3β-acetoxy-23-diazo-21,24-dinorchol-6-en-22-one ( 1 ).     

Transformed steroids. 118. The geometric isomerism of 20-ethoxycarbonylhydrazones of 3β-hydroxy-16,17α-cyclopropanopregn-5-en-20-one

In the reaction of the 3β-acetate of 3β-hydroxy-3′H-cyclopropano[16,17α]pregn-5-en-20-one (I) with ethoxycarbonylhydrazine in AcOH at 20°C (exposure for up to 6 days), a chromatographically separable equilibrium mixture of the 20Z-ethoxycarbonylhydrazone of 3β-acetoxy-3′H-cyclopropano[16,17α]pregn-5-en-20-one (II), with mp 190–195°C, and the 20E-ethoxycarbonylhydrazone of 3β-acetoxy-3′H-cyclopropano[16,17α]pregn-5-en-20-one (III) with mp 186–193°C (ratio 2:1) is obtained. The geometric isomers obtained are distinguished by IR, PMR, and CD spectroscopy. It has been shown that the observed geometric isomerism takes place via an intermediate enehydrazine form.     

A New Ursene Type Triterpenoid from Crepis napifera

A new triterpenoid, urs-20-en-3β-acetoxy-22α-ol, and three known compounds 3β-acetoxy-amyrin, 3β-acetoxy-lupeol, lupeol were isolated from the leaves of Crepis napifera (Franch.) Babc. Their structures were determined by means of spectroscopic studies.     

Autooxidation of Δ17(20)-20-hydroxy derivatives of steroids. Synthesis of 3β-acetoxy-17α-hydroperoxy-16α-methylpregn-5-en-20-one and its reduction to 17α-hydroxy derivative

An efficient procedure was proposed for the synthesis of 3β-acetoxy-17α-hydroperoxy-16α-methylpregn-5-en-20-one. Optimal conditions were found for the combined process including 1,4-addition of methylmagnesium bromide at the Δ¹⁶-20-oxo fragment of dehydropregnenolone acetate and autooxidation of resulting bromomagnesium 3β-acetoxy-16α-methylpregna-5,17(20)-dien-20-olate. The subsequent reduction of the 17α-hydroperoxy group and hydrolysis of the 3β-acetoxy group afforded 17α-hydroxy-16α-methyl-substituted dehydropregnenolone acetate and its 3-hydroxy analog in high yield.     

Synthesis and 5α-reductase inhibitory activity of C₂₁ steroids having 1,4-diene or 4,6-diene 20-ones and 4-azasteroid 20-oximes

The synthesis and evaluation of 5α-reductase inhibitory activity of some 4-azasteroid-20-ones and 20-oximes and 3β-hydroxy-, 3β-acetoxy-, or epoxy-substituted C?? steroidal 20-ones and 20-oximes having double bonds in the A and/or B ring are described. Inhibitory activity of synthesized compounds was assessed using 5α-reductase enzyme and [1,2,6,7-3H]testosterone as substrate. All synthesized compounds were less active than finasteride (IC??: 1.2 nM). Three 4-azasteroid-2-oximes (compounds 4, 6 and 8) showed good inhibitory activity (IC??: 26, 10 and 11 nM) and were more active than corresponding 4-azasteroid 20-ones (compounds 3, 5 and 7). 3β-Hydroxy-, 3β-acetoxy- and 1α,2α-, 5α,6α- or 6α,7α-epoxysteroid-20-one and -20-oxime derivatives having double bonds in the A and/or B ring showed no inhibition of 5α-reductase enzyme.     

Abnormal Beckmann rearrangement in 23-hydroxyiminodiosgenin acetate

A new transformation of the spiroketal side chain of diosgenin is reported: treatment of 23-hydroxyiminodiosgenin acetate with phosphorous oxychloride in pyridine produced an abnormal Beckmann rearrangement directing to the cleavage of the spiroketal side chain and generating 23,24-bisnorchol-5-enic skeletons: (2′R)-3′-cyano-2′-methylpropyl 3β-acetoxy-16α-chloro-23,24-bisnorchol-5-en-22-oate as the main product, and small amounts of (2′R)-3′-cyano-2′-methylpropyl 3β-acetoxy-16β-hydroxy-23,24-bisnorchol-5-en-22-oate and vespertilin acetate.     

云南美登木内生真菌Phomopsis sp. Lz42的化学成分

从云南美登木内生真菌Phomopsis species Lz42的琼脂平板发酵物中分离得到2个倍半萜和5个麦角甾醇类化合物(1~7), 其中化合物1和2为新化合物. 应用波谱技术确定其结构为4-Deacetyl-10-oxo-dihydrobotrydial(1)和麦角甾-6,22-二烯-5α,8α-环二氧-3-甲酸酯(2).     

Steroidal quinoxalines

The treatment of 3β-hydroxy-16α-bromo-5α-androstan-17-one, 3β-acetoxy-16α-bromo-5-androsten-17-one and 21-bromo-5-pregnen-3β-ol-20-one with 4,5-dimethyl-o-phenylenediamine gave substituted quinoxalines. Hydrolysis of 3β-acetoxy-5-androsteno[16,17-b]-6′,7′-dimethylquinoxaline produced the corresponding 3β-hydroxy compound. 3-Oxo-4-androsteno[16,17-b]-6′,7′-dimethylquinoxaline was obtained by Oppenauer oxidation of the corresponding alcohol.     

Carbon-13 NMR spectra of some pentacyclic triterpenoids with the olean-12-ene and 18α-olean-12-ene skeleton

The ¹³C NMR spectra of some pentacyclic triterpenoids, 3β-acetoxy-11-oxo-olean-12-ene-30-oic acid methyl ester, 3β-acetoxy-11-oxo-olean-12-ene-29-oic acid methyl ester, the corresponding 11-desoxo methyl esters, 3β-acetoxy-11-oxo-18α-olean-12-en-30-oic acid methyl ester and 3β-acetoxy-11-oxo-18α-olean-12-en-29-oic acid methyl ester are discussed. The shielding data are interpreted in term of the different orientation of the carbomethoxy group and of the change in configuration at the D/E ring junction and are diagnostically valuable for the differentiation of the mentioned compounds.     

Synthesis of 5α-Iodo-6-one Steroids

Abstract: The synthesis of 5-iodo-5α-cholestan-6-one (6), its 3β-acetoxy-(7) and 3β-chloro-(8) analogues, 3β-acetoxy-5-iodo-5α-stigmastan-6-one (9) and its 3β-chloro-(10) analogue by the reacion of silver chromate-iodine and pyridine with the corresponding steroidal olefins (1-5) is described. The structures of these products have been established on the basis of their elemental, analytical and spectral data.     

Reaction of 5β,6β-epoxy-16α,17α-cyclohexapregnane with methylmagnesium iodide

On treatment with methylmagnesium iodide, 3β-acetoxy-5β,6β-epoxy-16α,17α-cyclo-hexapregnan-20-one undergoes 3-O-deacetylation along with the opening of the 5β,6β-epoxide ring to form 5α-methyl-6β-hydroxy steroid and the 6α-methyl-6β-hydroxy isomer, the 20-keto group remaining intact.     

Synthese eines steroidischen 17 β-Pyrrolinons. Partialsynthetische Versuche in der Reihe der Herzgifte. 10.Mitteilung

Synthesis of a steroidal 17 β-pyrrolinone We describe the synthesis of 4′-(3 β-hydroxy-androst-5-ene-17 β-yl)-3′-pyrrolin-2′-one (6) starting from 3β-acetoxy-21-hydroxy-pregn-5-ene-20-one (1).     

Transformed steroids. 141. Iodosobenzene diacetate for theα-hydroxylation of [17,16a]-2′-methyloxazoline derivatives of 20-ketosteroids

Using the [17,16a-d]-2′-methyloxazoline derivatives of 3β-hydroxypregn-5-en-20-one (I) as an example, the α-hydroxylation reaction has been studied with the use of rodosobenzene diacetate in a methanolic solution of NaOH as the α-hydroxylating reagent. The reaction took place successfully through the stage of the formation and isolation of the corresponding [17,16a-d]-2′-methyloxazoline derivative of 20, 20-dimethylpregn-15-ene-3β,21-diol (II), the dimethyl acetal protection of which was eliminated by acid hydrolysis in methanol. The results of physicochemical investigations and biological trials of the [17,16a-d]-2′-methyloxazoline derivatives of 21-hydroxy-21-acetoxy-20-ketosteroids obtained are given.     

Alkaloide aus Cortex Condurango

From the CH₂Cl₂ extract of the bark of Marsdenia cundurango Reichenb. fil. (Cortex Condurango) a mixture of basic compounds could be isolated. Repeated thin layer and column chromatography yealded two alkaloids in pure form. For Kondurangamin A, which would be the mayor alkaloid with a content of 0.0007%, the structure was determined as 3β, 14β,20-trihydroxy-11 α-nicotinoyloxy-12β-acetoxy-5α,14β-pregnane and for Kondurangamin B as 3β,11α,12β,14β-tetrahydroxy-20-nicotinoyloxy-5α,14β-pregnane.     

Photochemical Rearrangement of a Steroidal α,β-Epoxylactone. Photochemical reactions,XI [1]

The UV. irradiation of 17β-acetoxy-4α, 5α-epoxy-2-oxaandrostan-3-one ( 7 ) yields 17β-acetoxy-2-oxa-10(5 → 4)abeo-4ζ (H)-androsta-3,5-dione ( 11 ). A non-photochemical synthesis of 11 , proceeding in lower yield, is also described.     

黑鳗藤中C_(21)甾体苷的分离和结构测定

从萝藦科植物黑鳗藤[Stephanotis mucronta (Blanco) Merr.]的藤茎中分离 到三个C_(21)甾体去氧糖苷（1） - （3）。通过化学降解和波谱技术，确定它们 的化学结构依次为：12-O-惕各酰基-20-O-乙酰基肉珊瑚苷元3-O-β-黄夹吡喃糖基 -（1→4）-β-磁麻吡喃糖基-（1→4）-β-磁麻吡喃糖苷（1），5，6-双氢-12-O- 乙酰基-20-O-惕各酰基肉珊瑚苷元3-O-β-黄夹吡喃糖基-（1→4）-β-磁麻吡喃糖 基-（1→4）-β-磁麻吡喃糖基（2）；12-O-乙酰基-20-O（N-甲基）邻氨基苯甲酰 基肉珊瑚甘元3-O-β-黄夹吡喃糖基-（1→4）-β-磁麻吡喃糖基-（1→4）-β-磁 麻吡喃糖甘（3）。其中1和2为新化合物，分别命名为mucronatoside A， mucrontoside B。3为已知化合物stephanoside E，系首次从该植物中分离得到。     

Synthetic Studies towards Pheromones by Cyanide-Catalyzed Ring Transformation of α-Hydroxy-β-oxoesters to δ-Valerolactones

The cyanide-catalyzed ring-transformation of α-hydroxy-β-oxoesters to δ-lactones with exocyclic ester moiety is the key transformation for the preparation of racemic 5-hexadecanolide (15 % over nine steps) and 6-acetoxy-5-hexadecanolide (22 % over eight steps), two insect pheromones. The benzyloxycarbonyl moiety is transformed via the acid chloride to the undecanoyl side chain. After reduction of the ketone to the secondary alcohol, this functional group was either reduced via the chloro compound to furnish the 5-hexadecanolide. On the other hand, stereoselective reduction of the ketone gave secondary alcohol with the wrong relative configuration, which was established by X-ray single-crystal structure. Inversion was achieved by reaction of the methanesulfonate with cesium acetate yielding (R*,S*)-6-acetoxy-5-hexadecanolide with the relative configuration also present in the natural product.     

"Alpha"-, "beta"- and "delta"-anhydrodigitoxigenin

The syntheses of 3β-hydroxy-5β-carda-14, 20:22-dienolide (= «β»-anhydro-), 3β-hydroxy-5β-carda-8:14, 20:22-dienolide (= «α»-anhydro-) and «δ»-anhydro-digitoxigenin (= probably 3β-hydroxy-5β, 14β-carda-8, 20:22-dienolide) by the best ways known to date, have been described. «δ»-Anhydro-digitoxigenin represents the thermodynamically most stable isomer. In this isomer the double bond in position 8 is unaffected by hydrogenation with Pt in acetic acid; with perbenzoic acid an epoxide results from which, on hydrogenation, the double bond can be regenerated in its original position. Analogous reactions are known to occur in the 8:14-epoxides.     

Herstellung von 3-Oxo-17β-hydroxy-1,19-cyclo-5α-androstan. Über Steroide, 219. Mitteilung

Under the influence of radical anions generated from lithium and biphenyl, 3-oxo-17β-acetoxy-19-mesyloxy-Δ¹-5α-androstane was converted into 3-oxo-17β-acetoxy-1, 19-cyclo-5α-androstane.