1957

DOI: 10.1021/jo01352a619

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Communications - Steroids. LXXXIV. Synthesis of 6-Methyl Hormone Analogs.

Howard J. Ringold¹,

G. Rosenkranz³

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Cited by 44 publications

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“…using firstly benzene, and then benzene-ether (5:l) as developing solvents. The 28- (2-(1,3-dithiany1))-5a-cholestan-3a-01 (2) …”

Section: Methodsmentioning

confidence: 99%

“…The possibilities of achieving a satisfactory general method for introducing substituents into the steroid nucleus by exploiting the properties of epoxides was drawn to our attention by the previous application of the reactions of As-epoxides with Grignard reagents (2)(3)(4)(5). Disappointingly, this approach to the stereospecific introduction of alkyl groups did not 'For part XI1 see ref.…”

mentioning

confidence: 99%

See 1 more Smart Citation

Steroids and Steroidases. XIII. Illustrations of the Potential of Lithiodithiane–Epoxide Reactions for the Stereospecific Introduction of Substituents into the Steroid Nucleus

1972

Can. J. Chem.

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The reactions of 2-lithio-1,3-dithiane with both 2c(,3c(-and 2/l,3/l-oxiranyl-5cc-cholestane have been used to prepare both epimers of 2-methyl-3-0x0-and 3-methyl-2-0x0-5a-cholestane. The results obtained illustrate the potential of the dithiane-epoxide route as an attractive and versatile general procedure for the stereospecific introduction of substituents into alicyclic compounds. Furthermore, since for six-membered ring compounds the epoxide ring is opened in a trans-diaxial manner, the substituent is introduced into the thermodynamically less stable orientation. Subsequent isomerization to the preferred equatorial isomer is thus possible and accordingly, both epimers are obtainable from the same synthetic sequence.On a utilisi' les reactions du 2-lithio-l,3-dithiane avec le 2a,3a-et le 2/l,3~-oxyranyl-5a-cholestane pour preparer les epimeres du 2-methyl-3-0x0-et du 3-methyl-2-0x0-5a-cholestane. Les resultats obtenus illustrent le potentiel du dithiane-epoxyde comme ttant une procedure generale attractive et versatile pour I'introduction sttreosptcifique de substituants dans les composes alicycliques. De plus, puisque le noyau epoxyde, de f a~o n trans-diaxiale pour les composts possedant un cycle a six, le substituant est introduit dans I'orientation la moins stable au point de vue thermodynamique. L'isomtrisation subsequente en isomere equatorial plus stable est alors possible e t a partir de cela, les deux epimeres peuvent itre obtenus a partir de la m&me sequence de synthtse.Canadian Journal of Chemistry, 50, 810 (1972) As a result of our interest in the mechanism of action of the A5+A4-3-ketoisomerase of P. testosteroni (la. b) we became interested in , , , developing convenient and versatile routes to stereospecifically substituted steroids suitable for "mapping" the active site of the enzyme. Of the general routes surveyed those based on a lithiodithiane-epoxide reaction appeared the most attractive and examples of the feasibility and advantages of this approach have been reported in communication form (lc). This note records the experimental and other details omitted from the preliminary communication since it is now apparent that the human resources required to continue the project as originally planned are unlikely to become available in the foreseeable future.The possibilities of achieving a satisfactory general method for introducing substituents into the steroid nucleus by exploiting the properties of epoxides was drawn to our attention by the previous application of the reactions of As-epoxides with Grignard reagents (2-5). Disappointingly, this approach to the stereospecific introduction of alkyl groups did not 'For part XI1 see ref. la. prove to be universally applicable since when the epoxide was not located at a ring junction, ring contraction predominated with both steroidal (6) and cyclohexene oxide (7) reactiom2 However, the fact that the latter compound underwent the expected ring opening with 2-lithio-1,3-dithiane (9a, b) indicated that similar reactions could be expected in the ...

“…using firstly benzene, and then benzene-ether (5:l) as developing solvents. The 28- (2-(1,3-dithiany1))-5a-cholestan-3a-01 (2) …”

Section: Methodsmentioning

confidence: 99%

“…The possibilities of achieving a satisfactory general method for introducing substituents into the steroid nucleus by exploiting the properties of epoxides was drawn to our attention by the previous application of the reactions of As-epoxides with Grignard reagents (2)(3)(4)(5). Disappointingly, this approach to the stereospecific introduction of alkyl groups did not 'For part XI1 see ref.…”

mentioning

confidence: 99%

Steroids and Steroidases. XIII. Illustrations of the Potential of Lithiodithiane–Epoxide Reactions for the Stereospecific Introduction of Substituents into the Steroid Nucleus

1972

Can. J. Chem.

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The reactions of 2-lithio-1,3-dithiane with both 2c(,3c(-and 2/l,3/l-oxiranyl-5cc-cholestane have been used to prepare both epimers of 2-methyl-3-0x0-and 3-methyl-2-0x0-5a-cholestane. The results obtained illustrate the potential of the dithiane-epoxide route as an attractive and versatile general procedure for the stereospecific introduction of substituents into alicyclic compounds. Furthermore, since for six-membered ring compounds the epoxide ring is opened in a trans-diaxial manner, the substituent is introduced into the thermodynamically less stable orientation. Subsequent isomerization to the preferred equatorial isomer is thus possible and accordingly, both epimers are obtainable from the same synthetic sequence.On a utilisi' les reactions du 2-lithio-l,3-dithiane avec le 2a,3a-et le 2/l,3~-oxyranyl-5a-cholestane pour preparer les epimeres du 2-methyl-3-0x0-et du 3-methyl-2-0x0-5a-cholestane. Les resultats obtenus illustrent le potentiel du dithiane-epoxyde comme ttant une procedure generale attractive et versatile pour I'introduction sttreosptcifique de substituants dans les composes alicycliques. De plus, puisque le noyau epoxyde, de f a~o n trans-diaxiale pour les composts possedant un cycle a six, le substituant est introduit dans I'orientation la moins stable au point de vue thermodynamique. L'isomtrisation subsequente en isomere equatorial plus stable est alors possible e t a partir de cela, les deux epimeres peuvent itre obtenus a partir de la m&me sequence de synthtse.Canadian Journal of Chemistry, 50, 810 (1972) As a result of our interest in the mechanism of action of the A5+A4-3-ketoisomerase of P. testosteroni (la. b) we became interested in , , , developing convenient and versatile routes to stereospecifically substituted steroids suitable for "mapping" the active site of the enzyme. Of the general routes surveyed those based on a lithiodithiane-epoxide reaction appeared the most attractive and examples of the feasibility and advantages of this approach have been reported in communication form (lc). This note records the experimental and other details omitted from the preliminary communication since it is now apparent that the human resources required to continue the project as originally planned are unlikely to become available in the foreseeable future.The possibilities of achieving a satisfactory general method for introducing substituents into the steroid nucleus by exploiting the properties of epoxides was drawn to our attention by the previous application of the reactions of As-epoxides with Grignard reagents (2-5). Disappointingly, this approach to the stereospecific introduction of alkyl groups did not 'For part XI1 see ref. la. prove to be universally applicable since when the epoxide was not located at a ring junction, ring contraction predominated with both steroidal (6) and cyclohexene oxide (7) reactiom2 However, the fact that the latter compound underwent the expected ring opening with 2-lithio-1,3-dithiane (9a, b) indicated that similar reactions could be expected in the ...

“…Deketalization with acetone and p-toluenesulphonic acid (22) afforded 3P,5cu-dihydroxy-BP-methylpregnan-20-one (LX), which was converted directly to the acetate IXa. The structure of the intermediates V, I X , and IXa was confirmed by oxidation, with chromic acid and sulphuric acid in acetone (26,27), of the dihydroxy ketone I X to the known (28,29) 5a-hydroxy-6P-methylpregnane-3,20-dione (XIII). Since this diketone XI11 is readily converted to 6a-methylprogesterone (XIV) (and also to its 60-epimer) (28, 29, cf.…”

mentioning

confidence: 90%

“…3 and 19). The structure and the stereochemistry of the slieleton were proved by reduction of the progesterone derivative X I I , with zinc and acetic acid, to 6a-methylprogesterone (XIV) (28,29)' and was further confirmed by dehydrobromination with dimethylformamide and lithium chloride (cf. ref.…”

mentioning

confidence: 95%

STEROIDS AND RELATED PRODUCTS: XXI. THE SYNTHESIS OF 17α-Bromo-6α -METHYLPROGESTERONE

1963

Can. J. Chem.

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The synthesis fo 17a-bromo-6a-inethylprogesterone, from pregnenolone acetate, is reported. The product is a potent luteoid with marked oral activity. In the course of this investigation, a useful x ariation of the synthesis of 6a-methylprogesterone, from pregnenolone, was devised. The rearrangement of a 5p,Bp-epoxide to a 6-ketone, upon chromatography on a l u n~i~l u m oxide "\Voelrn", was observed.

“…In addition to the aromatase inhibiting properties of 6α‐methylandrost‐4‐ene‐3,17‐dione studied by Numazawa et al .,11, 12 6α‐methylandrost‐4‐enes are described to show higher myotrophic and similar androgenic activity compared to their non‐methylated analogues 13, 14…”

mentioning

confidence: 95%

6α‐Methylandrostenedione: gas chromatographic mass spectrometric detection in doping control

Parr¹,

et al. 2008

Rapid Comm Mass Spectrometry

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In recent years products containing 6alpha-methylandrost-4-ene-3,17-dione have appeared on the sport supplement market. Scientific studies have proven aromatase inhibition and anabolic and mild androgenic properties; however, no preparation has been approved for medical use up to now. In sports 6alpha-methylandrost-4-ene-3,17-dione has to be classified as a prohibited substance according to the regulations of the World Anti-Doping Agency (WADA). For the detection of its misuse the metabolism was studied following the administration of two preparations obtained from the Internet (Formadrol and Methyl-1-Pro). Several metabolites as well as the parent compounds were synthesized and the structures of 3alpha-hydroxy-6alpha-methyl-5beta-androstan-17-one, 6alpha-methylandrost-4-ene-3,17-dione, and 5beta-dihydromedroxyprogesterone were confirmed by nuclear magnetic resonance (NMR) spectroscopy. The main metabolite, 3alpha-hydroxy-6alpha-methyl-5beta-androstan-17-one, was found to be excreted as glucuronide and was still detectable in microg/mL amounts until urine collection was terminated (after 25 h). Additionally, samples from routine human sports doping control had already tested positive for the presence of metabolites of 6alpha-methylandrost-4-ene-3,17-dione. Screening analysis can be easily performed by the existing screening procedure for anabolic steroids using 3alpha-hydroxy-6alpha-methyl-5beta-androstan-17-one as target substance (limit of detection <10 ng/mL). Its discrimination from the closely eluting drostanolone metabolite, 3alpha-hydroxy-2alpha-methyl-5alpha-androstan-17-one, is possible as the mono-TMS derivative.

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