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Synthesis of Bridged Oxafenestranes from Pleuromutilin
Author(s) -
Hicklin Robert W.,
López Silva Tania L.,
Hergenrother Paul J.
Publication year - 2014
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201404765
Subject(s) - tetracoordinate , chemistry , stereochemistry , molecule , planarity testing , carbocation , carbon atom , cis–trans isomerism , crystallography , ring (chemistry) , medicinal chemistry , organic chemistry , computer graphics (images) , computer science , planar
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.