Steroids. VII.<sup>1</sup> Contribution to the Bromination of ▵<sup>4</sup>-3-Ketosteroids and a New Partial Synthesis of the Natural Estrogens

Djerassi, Carl; Rosenkranz, G.; Romo, J.; Kaufmann, St.; Pataki, J.

doi:10.1021/ja01166a055

Cited by 90 publications

(30 citation statements)

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“…Bromination of 1 with 10 eq of Br 2 in AcOH-Et 2 O at room temperature for 10 min according to the method reported by Djerassi et al 12) gave 2a,6b-(2) and 2a,6a-dibromo-17b-acetoxyandrost-4-en-3-one (3) in yields of 37 and 50%, respectively (Table 1, run 1). The reaction of 1 with 1 eq of Br 2 at room temperature for 1 h gave 2 and 3 in yields of 11 and 14%, respectively, together with the recovery (56%) of 1 (run 2).…”

Section: Resultsmentioning

confidence: 93%

“…Reactions of 1 with Br 2 in AcOH-Et 2 O Compound 1 was reacted with 10, 1, and 5 eq of Br 2 in AcOH-Et 2 O according to the procedure described by Djerassi et al 12) These results are listed in Table 1 (runs 1-3). Reaction of 1 with 10 eq of Br 2 in the Presence of AgOTf To a solution of 1 (2.0 g, 6.06 mmol) in dry benzene (10 ml), Br 2 (3.0 ml, 60 mmol) and AgOTf (1.8 g, 7.0 mmol) were added, and the mixture was stirred at room temperature for 12 h. The reaction mixture was poured into cold water (50 ml) and extracted with CH 2 Cl 2 (3ϫ50 ml).…”

Section: Methodsmentioning

confidence: 99%

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Brominations of Steroidal Hormone Having .ALPHA.,.BETA.-Unsaturated Ketone, 17-O-Acetyltestosterone, in the Presence of Silver Triflate.

Shimizu

Tobari

Koyanagi

et al. 2001

CHEMICAL & PHARMACEUTICAL BULLETIN

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Bromination of 17-O-acetyltestosterone (17b b-acetoxyandrost-4-en-3-one) (1) was performed with 1, 5, and 10 eq of Br 2 in AcOH-Et 2 O at room temperature. In all cases 2a a,6b b-(2) and 2a a,6a a-dibromo-17b b-acetoxyandrost-4-en-3-one (3) were obtained, although the yields were dependent upon the conditions used. Bromination of compound 1 with 10 eq of Br 2 in the presence of silver trifluoromethanesulfonate (silver triflate, AgOTf) at room temperature for 12 h gave 2,7a a-dibromo-(4) and 2,4,7a a-tribromo-17b b-acetoxy-3-hydroxy-1-methylestra-1,3,5(10)-triene-6-one (5). The formations of the products were inferred on the basis of products obtained under controlled brominations of 1 in the presence of AgOTf, and of those obtained by the brominations of compounds 9-13 also in the presence of AgOTf.

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Section: Resultsmentioning

confidence: 93%

Section: Methodsmentioning

confidence: 99%

Brominations of Steroidal Hormone Having .ALPHA.,.BETA.-Unsaturated Ketone, 17-O-Acetyltestosterone, in the Presence of Silver Triflate.

Shimizu

Tobari

Koyanagi

et al. 2001

CHEMICAL & PHARMACEUTICAL BULLETIN

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“…Dehydrohalogenation with coIlidine afforded ,6,1.4-androsta diene-3, 17 -dione which was aromatized to estrone in 15 to 20 per cent yield. Rosenkranz, Djerassi et al (13,14,15) reached this goal by th� series of reactions outlined in Figure 1. Thus it is now possible to prepare 6-dehy dro-estrone, estrone, equilenin, or their corresponding 17 -hydroxy deriva tives in good yield from either testosterone, �f-androstene-3,17-dione or �1.4-androstadiene-3, 17-dione.…”

Section: Partial Synthesis Of Steroidsmentioning

confidence: 99%

Biochemistry of Steroids

Lieberman¹,

Dobriner²

1951

Annu. Rev. Biochem.

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The unique role of the steroid hormones in nearly all phases of life has been established. With the discovery of the sex hormones in the early thirties, it seemed that the physiological action of steroids was primarily concerned with the phenomena of sex. With ' the discovery of the steroid hormones of the adrenal gland in the late thirties it was soon found that these compounds had a profound influence on metabolism and that this was also true of the so-called sex hormones. Progress in a steadily expanding area of investiga tion in biology, biochemistry, and medicine was handicapped by the lack of sufficient quantities of the adrenal hormones. These hormones were for all practical purposes not available because the chemical introduction of the biologically essentially C-ll oxygen function into the steroid nucleus had not been accomplished. As a result of the brilliant work of Reichstein, Kendall, Gallagher, and Wintersteiner in the middle forties, this objective was achieved and together with the further contributions· of these investiga tors, as well as the very significant achievements of Sarett, Miescher, Wallis, and Julian, the large scale preparation of the most important cortical hor mones became practicable. Fin ally, large amounts were made available for extensive investigations. At about the same time the adrenfll-stimulating hormone of the pituitary (ACTH) became available in sufficient amounts and in a usable stage of purity so that both hormones were at hand for the study of the essential physiological processes controlled by the internal secre tions of the adrenal. Within an extremely short time the epoch-making dis covery of Hench and Kendall of the effect of these hormones in arthritis was reported. These observations opened a new era in medicine, physiology and biochemistry, and it was recognized as such by the award of the Nobel prize to Reichstein, Kendall, and Hench in 1950. The number of investigations has increased rapidly during the last 1 The following abbreviations have been used in this review. It should be noted that, unless otherwise mentioned, reference has been made to the acetoxy derivatives of the adrenal hormones

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“…Djerassi and his co-workers at Syntex also made intensive use of Inhoffen's pyrolytic aromatization, [51] supplying a particularly attractive example in their preparation of estradiol from testosterone acetate (Scheme 7). [52] The blossoming of steroid chemistry, the growing importance of steroid synthesis in academia and industry and, not least, the role of the protagonists have since around 1990 been the subject of some in-depth meditations. [53] In the history of biologically active agents, as described by those directly involved, it is not uncommonly the case that the witnesses closest to the events do not necessarily speak with the greatest reliability.…”

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confidence: 99%

Hans Herloff Inhoffen in His Times (1906−1992)

Quinkert

2004

Eur J Org Chem

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Steroids. VII.¹ Contribution to the Bromination of ▵⁴-3-Ketosteroids and a New Partial Synthesis of the Natural Estrogens

Cited by 90 publications

References 0 publications

Brominations of Steroidal Hormone Having .ALPHA.,.BETA.-Unsaturated Ketone, 17-O-Acetyltestosterone, in the Presence of Silver Triflate.

Brominations of Steroidal Hormone Having .ALPHA.,.BETA.-Unsaturated Ketone, 17-O-Acetyltestosterone, in the Presence of Silver Triflate.

Biochemistry of Steroids

Hans Herloff Inhoffen in His Times (1906−1992)

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Steroids. VII.1 Contribution to the Bromination of ▵4-3-Ketosteroids and a New Partial Synthesis of the Natural Estrogens

Cited by 90 publications

References 0 publications

Brominations of Steroidal Hormone Having .ALPHA.,.BETA.-Unsaturated Ketone, 17-O-Acetyltestosterone, in the Presence of Silver Triflate.

Brominations of Steroidal Hormone Having .ALPHA.,.BETA.-Unsaturated Ketone, 17-O-Acetyltestosterone, in the Presence of Silver Triflate.

Biochemistry of Steroids

Hans Herloff Inhoffen in His Times (1906−1992)

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Product

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Steroids. VII.¹ Contribution to the Bromination of ▵⁴-3-Ketosteroids and a New Partial Synthesis of the Natural Estrogens