Oxidative 10-membered ring expansion and contraction of stereoisomeric 1(10)-unsaturated and 1,10-epoxy-5-oxo-5,10-secosteroids induced by peracids
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AuthorsBjelaković, Mira S.
Krstić, Natalija M.
Pavlović, Vladimir D.
Article (Published version)
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The present study is concerned with the oxidative behaviour of unsaturated and epoxy 5-oxo-5,10-secosteroids in the presence of m-CPBA or TFAA-UHP as oxidants in order to investigate potential parameters controlling the chemoselectivity and regioselectivity. In the study we discovered a striking difference in the chemical behaviour of stereoisomeric compounds, (Z)- and (E)-3 beta-acetoxy-5,10-secocholest-1(10)-en-5-ones, as well as 1S,10R- and 1R,10R-epoxides. The secoketones were oxidized with exclusively C-6 migration and Baeyer-Villiger rearrangement product formation, whereas their stereoisomers provided the ring-contracted products, without lactone formation. The preferred conformation of expanded and contracted rings was established by NOESY correlations. The structures of two obtained lactones were also confirmed by X-ray analysis. The mechanistic and stereochemical aspects of these transformations are discussed. (C) 2012 Elsevier Ltd. All rights reserved.
Keywords:5-Oxo-5,10-secosteroids / 5,10-Secosteroidal 5,6-lactones / m-CPBA / TFAA-UHP reagent / Baeyer-Villiger oxidation
Source:Tetrahedron, 2012, 68, 36, 7479-7488
- Pergamon-Elsevier Science Ltd, Oxford