Process for the manufacture of .DELTA..sup.16 -steroid-14.beta.,

Chemistry of carbon compounds – Miscellaneous organic carbon compounds – C-metal

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26023957, 2602395, 2603975, C07J 4100

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active

039622177

ABSTRACT:
The invention is for a selective reduction of the 20- oxo group in .DELTA..sup.16 -steroid-14.beta.,18-diol-20-ones of the pregnane series to form the two epimeric 20-alcohols having the 20 S and 20 R configuration. The process is especially intended for the manufacture of alkaloids of the batrachotoxin type, particularly for batrachotoxinine A, which is a pregnane derivative having a 20 S alcohol grouping, and epimers and derivatives, such as epi-batrachotixinine A or 7,8-dihydrobatrachotoxinine A. The process is characterized by reducing the said .DELTA..sup.16 -steroid-14.beta.,18-diol-20-ones in form of their 14,18-ketals, for instance the 14,18 acetonides and using appropriate complex light metal hydrides and operating at appropriate temperatures. The separation of the two isomers is easy and can be effected by the usual physical operations, such as crystallization or chromatography. In the 14.beta.,18,20-triols obtained the 18-hydroxy group can be dehydrogenated to the corresponding 18-aldehydes, which are intermediates necessary in the synthesis of the said pharmacological interesting substances, such as batrachotoxin, by treatment with a sulphoxide in the presence of a carboxylic acid anhydride.

REFERENCES:
patent: 3781271 (1973-12-01), Wehrli et al.
Graf et al., "Helv. Chim. Acta," vol. 54 (1971) pp. 2789-2792.
"Steroid Reactions" by Djerassi et al., p. 141, relied on.

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