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Solid-phase Synthesis of [4.4] Spirocyclic Oximes
Published on: February 6, 2019
Synthesis of bridged oxafenestranes from pleuromutilin
Robert W Hicklin1, Tania L López Silva, Paul J Hergenrother
1Department of Chemistry, University of Illinois at Urbana-Champaign, 261 RAL, Box 36-5, 600 S. Mathews, Urbana, IL 61801 (USA).
Abstract:
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.
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