Elsevier

Tetrahedron

Volume 27, Issue 11, 1971, Pages 2293-2302
Tetrahedron

Transferreaktionen mit hilfe von bleitetraacetat—V: Eine neue methode zur gewinnung von α-azidosteroidketonen mittels Pb(OAC)4-n(N3)n

https://doi.org/10.1016/S0040-4020(01)91627-8Get rights and content

Zusammenfassung

Die Umsetzung der zweifach verzweigten Steroidolefine 1-5 mit dem System Pb(OAc)4-(CH3)3SiN3 bei −20°C führt zu den α-Azidosteroidketonen 1a-5a mit der Azidgruppe in axialer Stellung. Die aus den Δ2-Steroiden entstehenden Azidoketone 1a-3a können an Kieselgel in die entsprechenden β-Epimeren 1b-3b umgewandelt werden. Δ6-Cholesterinacetat (5) liefert neben dem Azidoketon 5a noch 7α-Azido-3β-acetoxy-cholest-5-en 6 und 7-Ketocholesterylacetat 7.

Abstract

The reaction of the twofold branched steroidolefines 1-5 with the system Pb(OAc4-(CH3)3SiN3 at a temperature of −20°C yields the α-azidoketones. 1a-5a with the azido group in an axial position. The 3α-azido-2-oxo-steroids 1a-3a can be transformed at silicagel surface into the epimeric 3β-azido-2-oxosteroids 1b-3b. Furthermore, the by-products 7α(-azido-3β-OAc-cholest-5-en 6 and 3β-OAc-7-oxo-cholest-5-en 7 are formed by the reaction of 5 with the title system.

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