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Apparent Failure of the Wharton Rearrangement in a Tricyclo[7.1.1.0 2,7 ]undecane
Author(s) -
Thomas Alan F.,
Di Giorgio Roberto,
Guntern Olivier
Publication year - 1989
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.19890720417
Subject(s) - chemistry , undecane , steric effects , alcohol , carroll rearrangement , medicinal chemistry , cope rearrangement , stereochemistry , sigmatropic reaction , organic chemistry
The Wharton rearrangement of 2,3‐epoxytricyclo[7.1.1.0 2,7 ]undecan‐3‐one, a sterically hindered system, which should have led to an allyl alcohol with the OH group at a bridgehead, gave instead the allylically rearranged alcohol. The desired hydroxy compound was prepared by the Barton modification of the Wharton rearrangement: borohydride reduction to the epoxy alcohols, reaction with N , N ′‐thiocarbonylbisimidazole, and treatment with Bu 3 SnH. The bridgehead alcohol (and other 2‐oxygenated tricyclo[7.1.1.0 2,7 ]undecanes) readily rearranged under acidic or thermal conditions.
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