Zur Kenntnis der Sexualhormone II. Über die Synthese des Testikelhormons (Androsteron) und Stereoisomerer desselben durch Abbau hydrierter Sterine

Růžička, L.; Goldberg, M. W.; Meyer, Jules; Brüngger, H.; Eichenberger, E.

doi:10.1002/hlca.193401701170

Cited by 91 publications

(4 citation statements)

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“…4H NMR spectroscopy showed the intermediate 6 derived from 2 to have incorporated both the steroid and triphenylphosphine moieties in a 1:1 ratio, with no incorporation of diethyl azodicarboxylate derived fragments. The stereochemistry at the steroid carbinol carbon remained unchanged from that of the starting alcohol 2, as shown by the half bandwidth of the 3/3 (axial) hydrogen (20)(21)(22)(23)(24)(25)(26)(27)(28)(29)(30); however, the 3 H resonance was shifted downfield to approximately 4.5 ppm, in agreement with the literature9 value of 4.35 ppm for the corresponding proton in (cyclohexyloxy)triphenylphosphonium triflate. The corresponding intermediate isolated from the reaction of 3/3-cholestanol ( 7) was shown to be a phosphonium salt by the 31P NMR resonance at +59.2 ppm (CD-Cl3), in good agreement with that observed in the above NMR studies.…”

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confidence: 99%

A revised mechanism for the Mitsunobu reaction

1987

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A revised mechanism for the Mitsunobu reaction

1987

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“…The 5B-cholestan-3-one was isolated by means of preparative thin layer chromatography with Kieselgel G (Merck, Darmstadt, Germany) as adsorbent and benzene-ethyl acetate (85: 15, v/v), as solvent. Crystallization from a methanol-ethyl acetate mixture yielded 26 mg of [4B-3H,4-14C]5B-cholestan-3-one, m. p. 58", reported m. p. 61-62' [13]. The ratio of 3H to 14C was 2.7 ( Table 2).…”

Section: Methodsmentioning

confidence: 99%

Stereochemistry of the Enzymatic Conversion of a Δ⁴‐3‐Oxosteroid into a 3‐Oxo‐5β‐Steroid

Björkhem

1969

European Journal of Biochemistry

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The synthesis of [4-3H,4-14C]7.cr-hydroxycholest-4-en-3-one is described. The transformation of this compound into cholic acid in the bile fistula rat occurred with retention of the tritium label. The position of the tritium label in the isolated cholic acid was established by oxidation at the C-3 position of the methylated derivative followed by dehydrogenation with selenium dioxide yielding methyl 7a,12a-dihydroxy-3-oxo-chol-4-enoate. This compound retained most of the tritium label. Since selenium dioxide dehydrogenation of a 3-oxo-5p-steroid could be shown to involve a preferential loss of a 4a-hydrogen, it was concluded that the tritium label in the cholic acid isolated from bile was located in the 4/3-position. The enzymatic reduction of the A4 double bond in 7a-hydroxycholest-4-en-3-one in its conversion into cholic acid thus involves a trans diaxial addition of hydrogens.The conversion of cholesterol into bile acids entails the intermediary formation of 7a-hydroxycholest-4-en-3-one and 7a, 12a-dihydroxycholest-4-en%one and of the corresponding 3-oxo-5P-steroids [I].The saturation of the A4 double bond is catalyzed by a soluble A4-3-oxosteroid 5b-reductase(s) [2,3]. The reaction was shown recently to involve the transfer of a hydride ion from the A-side of NADPH to the 5P-position of the steroid and the addition of a proton to the 4-position [4]. The stereochemistry of the addition o€ the proton was not established. The present communication provides evidence that the proton is introduced into the 4a-position. The saturation of the A4 double bond in the biosynthesis of bile acids is thus a trans diaxial addition of hydrogens. Wettstein 161. The reaction mixture was acidified with 0.5M sulfuric acid and was extracted with ether. The ether extract was washed with 0.5M sulfuric acid, with a 5 O l 0 solution of sodium hydroxide (wlv), and with water until neutral. The ether extract was evaporated to dryness under reduced pressure and the residue was chromatographed on a column of 15 g of aluminum oxide, grade I11 (Woelm, Eschwege, Germany). The column was eluted with increasing concentrations of benzene in hexane. Benzene in hexane, 500/, (vlv), eluted 65 mg of [4-3H,4-14C]cholest-4,6-dien-3-one. The material was crystallized from a methanol-water mixture yielding 57 mg, m. p. 78", reported m. p. 80-81" [7]. The ratio of 3H to 14C was 1.8 (Table 1). R X P E R I M E N T A L PROCEDURE Materials(4-3H,4-14G]7a-Hydroxycholest-4-en-3-one. [4-3H, 4-14C]Cholest-4,6-dien-3-one, 56 mg, was dissolved in 3.5 ml of chloroform and 2 ml of a solution of monoperphthalic acid in ether (30mg/ml) were added [S, 91. The mixture was allowed to stand a t room temperature for 20hours. The reaction mixture was then poured into a 5 0 / / , solution of sodium bicarbonate in water (w/v) and the mixture was extracted with ether. The ether extract was washed with water until neutral and the solvent was evaporated. The residue of the ether extract was chromatographed on a column of l o g of aluminum oxide, gradeIII. The column was elute...

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“…184-185°, [<*]" +95°(ethanol), vm»x. 1736 cm.-1 and free hydroxyl band; reported (9): m.p. 182-183°, [a]" +94.6°(ethanol).…”

Section: Experimental4unclassified

“…However, when epiandrosterone p-toluenesulfonate (lb) [prepared (5) from isoandrosterone (la) in over 90% yield] was treated with sodium acetate in boiling acetic acid and acetic anhydride, it was converted to a mixture which was resolved readily by silica chromatography into A2-androsten-17-one (III) as major component (54 %)2 and androsterone acetate (Ila) as minor component (39%).3 The latter could be saponified quantitatively to androsterone (lib). The structures assigned to these substances follow from the elementary analyses, infrared spectra and the similarity of physical properties to those of the known compounds (1,7,9). Since A2-androsten-17-one (III) was the major product formed in the acetolysis step and changing the reaction conditions did not appreciably alter the ratio of III to Ila, it was highly desirable to effect the conversion of this A2-compound to androsterone.…”

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STEROIDS. LXV.¹ A SYNTHESIS OF ANDROSTERONE

Iriarte¹,

Rosenkranz²,

Sondheimer³

1955

J. Org. Chem.

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Comparatively large quantities of androsterone (lib) were required in these Laboratories for biological studies, and for this reason we became interested in developing a more efficient synthesis of lib than those hitherto reported (1). In the present paper we describe such a synthesis, which employs epiandrosterone (androstan-3jS-ol-17-one) (la) [easily obtained by catalytic hydrogenation (2) of the available A6-androsten-3/3-ol-l7-one acetate] as starting material and proceeds in co. 60 % over-all yield.

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Zur Kenntnis der Sexualhormone II. Über die Synthese des Testikelhormons (Androsteron) und Stereoisomerer desselben durch Abbau hydrierter Sterine

Cited by 91 publications

References 4 publications

A revised mechanism for the Mitsunobu reaction

A revised mechanism for the Mitsunobu reaction

Stereochemistry of the Enzymatic Conversion of a Δ⁴‐3‐Oxosteroid into a 3‐Oxo‐5β‐Steroid

STEROIDS. LXV.¹ A SYNTHESIS OF ANDROSTERONE

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Zur Kenntnis der Sexualhormone II. Über die Synthese des Testikelhormons (Androsteron) und Stereoisomerer desselben durch Abbau hydrierter Sterine

Cited by 91 publications

References 4 publications

A revised mechanism for the Mitsunobu reaction

A revised mechanism for the Mitsunobu reaction

Stereochemistry of the Enzymatic Conversion of a Δ4‐3‐Oxosteroid into a 3‐Oxo‐5β‐Steroid

STEROIDS. LXV.1 A SYNTHESIS OF ANDROSTERONE

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Stereochemistry of the Enzymatic Conversion of a Δ⁴‐3‐Oxosteroid into a 3‐Oxo‐5β‐Steroid

STEROIDS. LXV.¹ A SYNTHESIS OF ANDROSTERONE