TY - JOUR
T1 - Synthesis of bridged oxafenestranes from pleuromutilin
AU - Hicklin, Robert W.
AU - Lõpez Silva, Tania L.
AU - Hergenrother, Paul J.
N1 - Copyright:
Copyright 2014 Elsevier B.V., All rights reserved.
PY - 2014/9/8
Y1 - 2014/9/8
N2 - 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.
AB - 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.
KW - fenestranes
KW - natural products
KW - planar tetracoordinate carbon atom
KW - strained molecules
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U2 - 10.1002/anie.201404765
DO - 10.1002/anie.201404765
M3 - Article
C2 - 25045118
AN - SCOPUS:84906946560
SN - 1433-7851
VL - 53
SP - 9880
EP - 9883
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
IS - 37
ER -