Original scientific paper

Stereochemically Controlled Acetalizations in the Ten-Membered Ring of (Z)- and (E)-5,10-Seco-Steroidal Ketones

Ljubinka Lorenc ; Department of Chemistry, Faculty of Science, University of Belgrade, and Institute of Chemistry, Technology and Metallrgy, P. O. Box 550, 11001Belgrade, Yugoslavia
Milan Dabović ; Department of Chemistry, Faculty of Science, University of Belgrade, and Institute of Chemistry, Technology and Metallrgy, P. O. Box 550, 11001Belgrade, Yugoslavia
Vladimir Pavlović ; Department of Chemistry, Faculty of Science, University of Belgrade, and Institute of Chemistry, Technology and Metallrgy, P. O. Box 550, 11001Belgrade, Yugoslavia
Ivan Juranić ; Department of Chemistry, Faculty of Science, University of Belgrade, and Institute of Chemistry, Technology and Metallrgy, P. O. Box 550, 11001Belgrade, Yugoslavia
Jože Foršek ; Department of Chemistry, Faculty of Science, University of Belgrade, and Institute of Chemistry, Technology and Metallrgy, P. O. Box 550, 11001Belgrade, Yugoslavia

Abstract

(Z)-3~-Acetoxy-5,10-seco-cholest-l(10)-en-5-one2a reacts with
m-chloroperbenzoic acid to give the cis-(lS,10R)-epoxide 4, which,
under acid-catalyzed conditions, undergoes stereospecific intramolecular cyclization to afford the (lS,5S,10S)-acetal 5. On the
other hand, hydrolysis of the osmate ester of (E)-3~-acetoxy-
-5,10-seco-cholest-1(10)-en-5-one 3a (with aqueous hydrochloric
acid in methanol solution) produces two stereochemically different
acetal derivatives, i. e. the (1R,5R,10R)-product7 and (1S,5S,10S)-
-isomer 5, in ca. 49% and 28°/1 yields, respectively. The stereochemical course of these transformations is discussed in terms of the most stable ground-state conformations of the starting (Z)-
and (E)-seco-ketones (2a and 3a) in solution.

Keywords

Hrčak ID:

178040

URI

https://hrcak.srce.hr/178040

Publication date:

6.3.1986.

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