Synthesis of Bridged Oxafenestranes from Pleuromutilin |
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| Authors: | Robert W Hicklin Tania L López?Silva Prof Paul J Hergenrother |
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| Affiliation: | Department of Chemistry, University of Illinois at Urbana‐Champaign, 261 RAL, Box 36‐5, 600 S. Mathews, Urbana, IL 61801 (USA) |
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| 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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| Keywords: | fenestranes natural products planar tetracoordinate carbon atom strained molecules |
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