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Helvetica Chimica ActaVolume 82, Issue 5, 1999, Pages 707-721

13,14-seco-steroids: A new type of modified steroids containing a nine- membered ring(Article)

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  • aCenter for Chemistry, ICTM, P.O. Box 815, YU-11001 Belgrade, Serbia
  • bFaculty of Chemistry, University of Belgrade, Studentski trg 12-16, YU-11001 Belgrade, Serbia
  • cFaculté des Sciences, Dép. de Chimie, UCL, Place Pasteur 1, B-1348 Louvain-la-Neuve, Serbia
  • dLeimgrubenweg 21, CH-4102 Binningen, Serbia

Abstract

Oxidations of 14α-hydroxy-5α-cholestan-3β-yl acetate (5) with lead tetraacetate under thermal or photolytic conditions or in the presence of iodine proceed mainly by fragmentation of the C(13)-C(14) bond to give as the primary products the 13,18-didehydro-13,14-seco derivative 6 and the (E)- Δ 12 -13,14-seco ketone 11, respectively. Further transformations of these compounds under conditions of their formation afforded, in addition, the acetoxy derivatives 7-9 (from 6), and the D-homo-C-nor compound 12 and (12R,13R)-epoxide 13 (from 11). Unexpectedly, the photolytic lead- tetraacetate oxidation of 5 resulted partly (to ca. 20%) in a reversible fragmentation involving scission and recombination of the C(8)-C(14) bond followed by formation of the 14β,22-ether 10. Possible mechanisms for the observed transformations are discussed.

Indexed keywords

EMTREE drug terms:epoxidesteroid
EMTREE medical terms:articlecarbon nuclear magnetic resonancecolumn chromatographydiastereoisomerinfrared spectrometryoxidationphotolysisstructure analysisX ray analysisX ray crystallography
  • ISSN: 0018019X
  • CODEN: HCACA
  • Source Type: Journal
  • Original language: English
  • DOI: 10.1002/(SICI)1522-2675(19990505)82:5<707::AID-HLCA707>3.0.CO;2-O
  • Document Type: Article
  • Publisher: Verlag Helvetica Chimica Acta AG

  Lorenc, L.B.; Faculty of Chemistry, University of Belgrade, Studentski trg 12-16, Serbia
© Copyright 2019 Elsevier B.V., All rights reserved.

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