Mechanistic insights on the reactivity of furospirostanes with the 16β,22:22,25-diepoxy-23-acetoxymethyl-24-methyl side chain

•The reactivity of the 16β,22:22,25-diepoxy-23-acetoxymethyl moiety was studied.•Bromination at C-23 is accompanied by substitution of the 23′-acetoxy moiety.•Treatment with HBr in AcOH results in substitution of the 23′-acetoxy moiety.•Furospirostanes were characterized by combined 2D NMR technique...

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Bibliographic Details
Published in:Steroids 2013-09, Vol.78 (9), p.787-797
Main Authors: Macías-Alonso, Mariana, Flores-Álamo, Marcos, Iglesias-Arteaga, Martín A.
Format: Article
Language:English
Subjects:
Allylic substitution
Bromination
Bromodeacetoxylation
Catalysis
Crystallography, X-Ray
Elimination
Epoxy Compounds - chemical synthesis
Epoxy Compounds - chemistry
Furospirostanes
Halogenation
Magnetic Resonance Spectroscopy
Models, Molecular
Molecular Conformation
Spirostans - chemical synthesis
Spirostans - chemistry
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Summary:•The reactivity of the 16β,22:22,25-diepoxy-23-acetoxymethyl moiety was studied.•Bromination at C-23 is accompanied by substitution of the 23′-acetoxy moiety.•Treatment with HBr in AcOH results in substitution of the 23′-acetoxy moiety.•Furospirostanes were characterized by combined 2D NMR techniques and X-ray studies. F-ring opening in spirostanes with the 16β,22:22,25-diepoxy-23-acetoxymethyl-24-methyl side chain produces a Δ22-intermediate with an allylic acetoxy group. For this reason the reactivity profile of these compounds deviates from that observed in other naturally occurring or synthetic spirostanes and furospirostanes
ISSN:0039-128X
1878-5867
DOI:10.1016/j.steroids.2013.05.014