Fortschritte in der Totalsynthese von Steroiden

Velluz, L; Valls, J.; Nomine, G.

doi:10.1002/ange.19650770502

Cited by 64 publications

(18 citation statements)

References 76 publications

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“…Although the intermediates were never isolated in going from 213 to 216, it should be appreciated that the hydrogénation must have given appreciable amounts of the CD-trans product (see Section 12.1 for a discussion of this problem). The synthesis at this point intersected with many other plans; this precise compound had previously been prepared in an alternate fashion [35,142,143]. Thus, methyl 5-oxo-6-heptenoate (214) condensed with 2-methylcylcopentane-l,3-dione to give an 88% yield of 215.…”

Section: Hoffmann-laroche Approachmentioning

confidence: 90%

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Cd → BCD → Abcd

1974

Organic Chemistry: A Series of Monographs

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The starting CD intermediates for the various total syntheses outlined in this chapter and in Chapter 7 are often the same or quite analogous. Historically, a large effort has been expended in the preparation of such material, both in the context of steroid synthesis and, recently, as a goal unto itself. A discussion of the pathways developed for the synthesis of CD intermediates has been included at this point such that later, when the individual total synthetic schemes are presented, it will be unnecessary to outline the preparation of the starting materials, except in those cases where unique pathways have been developed.Most of the early synthetic plans started with appropriate naphthalene derivatives which in turn gave rise to D-homosteroids. For example, Johnson's estrone synthesis started with decalin-l,5-dione (3, Scheme 12-1) which had earlier been prepared from 1,5-dihydroxynaphthalene (58%) [1], By modifying the previously employed conditions to include Raney nickel hydrogénation at elevated temperatures and pressures in a basic ethanolic solution, it was possible to obtain a mixture of diols, 2 (stereochemistry undetermined), which, without purification, could be oxidized to a mixture of eis and trans diketones 3 [2], The yield for this conversion (l-»3) was 55% and, for synthetic purposes, the mixture 239 O OH J Φ-,ύ^.

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Section: Hoffmann-laroche Approachmentioning

confidence: 90%

“…In the first [169], the optically active trans hydrindane 244 [35,143] underwent a Leuckart reaction with ammonium bicarbonate to provide the expected tricyclic lactam as a mixture of the 9a-(72%) and 9/?-(26%) isomers. These compouds were easily separated by taking advantage of their rather marked solubility differences.…”

Section: Scheme 12-28mentioning

confidence: 99%

Cd → BCD → Abcd

1974

Organic Chemistry: A Series of Monographs

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“…These methods are solely of scientific interest and have no industrial importance. Although the large-scale corticoid total syntheses developed by Roussel -Uclaf have been improved considerably, they are still not as economical as the partially synthetic processes [203][204][205].…”

Section: Properties and Usesmentioning

confidence: 99%

Hormones

Sandow¹,

Scheiffele²,

Haring³

et al. 2000

Ullmann's Encyclopedia of Industrial Chemistry

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“…When heated in air it deflagrates with a bluish-white flame. The analogous reaction of N-(trimethy1silyl)sulfinylamine with bromine gives a difficultly separable mixture that contains N-bromosulfinylamine (2). However, (2) is formed quantitatively on treatment of stoichiometric amounts of bis(sulfinylamido)mercury[41 with bromine in trichlorofluoromethane a t room temperature.…”

Section: N-halosulfinylaminesmentioning

confidence: 99%

“…For the success of this pathway it was essential t o reduce 3-oxo-5(10)-estrenes ( I ) (which are readily obtainable by Birch reduction and subsequent enolether cleavage of steroids having an aromatic ring A) stereospecifically to 3P-hydroxy-5(10)-estrenes(2). This reduction gives only 15-20% yields when carried out with complex metal hydrides, hydrogen in the presence of a platinum catalyst, or according t o the Meerwein-Ponndorf method; the main products are 3cr-hydroxy-5(1O)-estrenes [4C, 51.…”

mentioning

confidence: 99%

Synthesis of Testosterones from Estrogens

Berndt¹,

Wiechert²

1969

Angew. Chem. Int. Ed. Engl.

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Not only many organic N-sulfinylamines [ I ] but also N-(trimethylsilyl)sulfinylamine[zl are known, the reactions of the latter being very similar to those of silyl pseudohalides. We have obtained bis(sulfinylamido)mercury(II) ( I ) as the first sulfinylamide of a metal by reaction of mercury(i1) fluoride with N-(trimethylsily1)sulfinylamine. The reaction proceeds quantitatively.Tetrahydrofuran is a particularly suitable solvent as ( I ) dissolves readily in it and can be recrystallized from it. 23 g of HgFz reacts with 27 g of (CH&SiNSO in 40-60 ml of boiling, stirred, dry T H F within 30 rnin in a strongly exothermic reaction. The amide ( I ) crystallizes as colorless needles, m.p. 128 "C (decomp.), but, if heating is too slow, decomposition sets in below the melting point. In contrast to most organic sulfinylamines, it is surprisingly stable to hydrolysis and alcoholysis. Compound ( I ) was identified by analysis and its mass spec-trumr31 [with reference to the isotope 202Hg: m / e = 326, Hg(NS0)2; 264, Hg(NS0); 202, Hg; 48, SO; 46, NS; 32, S]. The I R spectrum (Nujol) shows bands at 1250s, 1217s, 1078 s, 604 rn, 590 m, 561 m, 313 s, and 280 w cm-1.

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Fortschritte in der Totalsynthese von Steroiden

Cited by 64 publications

References 76 publications

Cd → BCD → Abcd

Cd → BCD → Abcd

Hormones

Synthesis of Testosterones from Estrogens

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