Autoxidation of steroid .DELTA.3,5-dien-3-ol ethers. A simple route to 6.beta.-hydroxy-4-en-3-tones

A One-Step Synthesis of 6β-Hydroxy-Δ4-3-ketones. Novel Oxidation of Homoallylic Sterols with Permanganate Ion

“…Mechanistically, further rearrangement may occur via the concomitant β-epoxidation of the Δ 5 double bond and oxidation of the 3β-hydroxy group, followed by epoxide ring opening and proton elimination at C-4 to yield the Δ 4 unsaturated ketone. Several synthetic methods have been reported for the synthesis of steroidal 6β-hydroxy-Δ 4 -3-ketones, but yields were moderate to low. , The oxidation with permanganate ion provides an alternative and streamlined synthesis of this type of structure in one step from commercially available starting materials.…”

Synthesis of 3α,6β,17,20α-tetrahydroxy-5β-pregnan-11-one 6-hemisuccinate, a hapten for immunoassay of 3α,17,20α-trihydroxy-5β-pregnan-11-one (‘pregnanetriolone’)

“…3,3-Ethylenedioxy-17,20a-isopropylidenedioxypregn-5-en-1 1one (14).-A solution of 17,20a-isopropylidenedioxypregn-4ene-3,ll-dione I ' (13) (324 mg) in 2-ethyl-2-methyl-1,3-dioxolane (6.0 ml) with toluene-p-sulphonic acid (6.0 mg) was slowly distilled under a gentle flow of nitrogen until the volume had been reduced to 1.5 ml. After cooling, a solution of sodium carbonate (30 mg) in water (7.5 ml) was added.…”

“…Another route to the title compound, aimed at introducing the 6P-hydroxy-5p-H features by a stereochemically unambiguous route, involved the hydroboration-oxidation of 3,3-ethylenedioxy-1 7,20a-isopropylidenedioxypregn-5-en-1 1-one ( 14) prepared in the usual way l 5 from 17,20a-isopropylidenedioxypregn-4-ene-3,ll-dione (13). Hydroboration of 3,3ethylenedioxy-5-enes is known to favour P-face addition for steric r e a ~o n s . '…”

Synthese von A‐Homo‐19‐norsteroiden. Über Steroide, 214. Mitteilung

“…Nach Abkiihlen, Abnutschen und Nachw-aschen rnit Toluol und Methylenchlorid wurde der Riickstand des im Vakuum eingedampften Filtrates an 390 g Aluminiumoxid (Aktivitat 11) chromatographiert. 4 u s den rnit Toluol-Essigester-(99 : 1)-und -(49: 1)-Gemisch eluierten Fraktionen erhielten wir durch Kristallisation aus einem Methylenchlorid-xther-11) Uber die Photoautoxydation von 3-A1k0xy-A~; ,-Steroiddienen zu 3-0xo-6,!-hydroxy-d4-Steroiden berichteten kiirzlich GARDI & LUSIGNANI [13].…”