Synthesis of Bridged Oxafenestranes from Pleuromutilin

Fenestranes are an intriguing class of highly strained molecules possessing a quaternary carbon with bonds that deviate from the canonical tetrahedral geometry. Herein we report the discovery that the natural product pleuromutilin can be used as a structurally complex starting material for the synth...

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Bibliographic Details
Published in:Angewandte Chemie 2014-09, Vol.126 (37), p.10038-10041
Main Authors: Hicklin, Robert W., López Silva, Tania L., Hergenrother, Paul J.
Format: Article
Language:eng ; ger
Subjects:
Bridging
Carbon
Cascades
Chemistry
Crystallography
Fenestrane
Gespannte Moleküle
Natural products
Naturstoffe
Planarer vierfach koordinierter Kohlenstoff
Planarization
Synthesis
X-rays
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Summary:Fenestranes are an intriguing class of highly strained molecules possessing a quaternary carbon with bonds that deviate from the canonical tetrahedral geometry. Herein we report the discovery that the natural product pleuromutilin can be used as a structurally complex starting material for the synthesis of a series of bridged cis,cis,cis,cis‐[4.5.5.5]‐ and cis,cis,cis,cis‐[4.5.7.5]oxafenestranes through a carbocation rearrangement cascade. X‐ray crystallographic analysis of several cis,cis,cis,cis‐[4.5.5.5]oxafenestranes shows a significant planarization of the central tetracoordinate carbon atom and demonstrates the influence of bridgehead substituents and bridging rings on planarity. Fenestrane sind stark gespannte Moleküle mit einem quartären Kohlenstoffatom, dessen Bindungen von der üblichen Tetraedergeometrie abweichen. Der Naturstoff Pleuromutilin kann für die Synthese von überbrückten [4.5.5.5]‐ und [4.5.7.5]Oxafenestranen über eine Carbokationenumlagerungskaskade verwendet werden. Röntgenkristallographische Untersuchungen zeigen, dass diese Verbindungen eine deutliche Planarität des zentralen vierfach koordinierten Kohlenstoffatoms aufweisen.
ISSN:0044-8249
1521-3757
DOI:10.1002/ange.201404765