Umwandlung von (20S)‐20‐(Hydroxymethyl)pregna‐1,4‐dien‐3‐on in (20S)‐20‐(p‐Toluolsulfonyloxymethyl)pregna‐1,5‐dien‐3β‐ol und ‐3α‐ol: Zwischenprodukte für Vitamin D‐Derivate

Umwandlung von (20S)‐20‐(Hydroxymethyl)pregna‐1,4‐dien‐3‐on in (20S)‐20‐(p‐Toluolsulfonyloxymethyl)pregna‐1,5‐dien‐3β‐ol und ‐3α‐ol: Zwischenprodukte für Vitamin D‐Derivate

Transformation of (20S)‐20‐(Hydroxymethyl)pregna‐1,4‐dien‐3‐one into (20S)‐20‐(p‐Toluene‐sulfonyloxymethyl)pregna‐1,5‐dien‐3β‐ol and ‐3α‐ol: Intermediates of Vitamin D Derivatives Efficient three‐step approaches to the two 3‐epimeric 22‐tosylated 1,5‐diene‐3,22‐diols 6 and 7 starting with (20S)‐20‐(...

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Veröffentlicht in:Journal für Praktische Chemie/Chemiker‐Zeitung 1996, Vol.338 (1), p.214-219
Hauptverfasser: Wittmann, S., Krieg, R., Prousa, R., Schönecker, B., Droescher, P.
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container_issue 1
container_start_page 214
container_title Journal für Praktische Chemie/Chemiker‐Zeitung
container_volume 338
creator Wittmann, S.
Krieg, R.
Prousa, R.
Schönecker, B.
Droescher, P.
description Transformation of (20S)‐20‐(Hydroxymethyl)pregna‐1,4‐dien‐3‐one into (20S)‐20‐(p‐Toluene‐sulfonyloxymethyl)pregna‐1,5‐dien‐3β‐ol and ‐3α‐ol: Intermediates of Vitamin D Derivatives Efficient three‐step approaches to the two 3‐epimeric 22‐tosylated 1,5‐diene‐3,22‐diols 6 and 7 starting with (20S)‐20‐(hydroxymethyl)pregna‐1,4‐dien‐3‐one (1) were developed and optimized. Isomerization of 1 to the 1,5‐dien‐3‐one 3 and subsequent tosylation furnished the deconjugated 3‐ketone 4. The 3β‐alcohol 6 was available from 4 by means of in situ generated calcium borohydride. Treatment of 4 with lithium trisiamylborohydride (LS‐Selectride) afforded the highest yield of the hitherto unknown 3α‐epimer 7. Following the optimized synthesis, 6 and 7 were obtained from 1 in 60 % and 50 % overall yield, respectively.
doi_str_mv 10.1002/prac.19963380145
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title Umwandlung von (20S)‐20‐(Hydroxymethyl)pregna‐1,4‐dien‐3‐on in (20S)‐20‐(p‐Toluolsulfonyloxymethyl)pregna‐1,5‐dien‐3β‐ol und ‐3α‐ol: Zwischenprodukte für Vitamin D‐Derivate
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