Transannular Claisen rearrangements of [alpha]-sulfonyl lactones
Author(s)
Gore, Sophie
Type
Thesis
Abstract
This thesis is divided into three sections.Section one is a review of transannular pericyclic reactions. It covers the four maintypes of pericyclic reaction and major contributions in the field to date. Recentapplications of these reactions to natural product synthesis are also included.Section two discusses the results of research efforts into transannular Claisenrearrangements of ?-sulfonyl lactones. The background to the project is discussedalong with initial investigations into the transannular Claisen and decarboxylativeClaisen rearrangements (dCr) of the 7-membered ?-tosyl lactone to form vinylcyclopropanes. Stereoselectivity from within the pericyclic array, by substitution at thelactone C7 position is examined. Efforts towards stereoinduction from outside of thepericyclic array are also detailed, along with aryl substitution at the lactone C5 positionto form highly substituted vinyl cyclopropanes. Extension of this methodology to theunprecedented transannular Claisen rearrangement and dCr reaction of 8-membered ?-tosyl lactones to give vinyl cyclobutanes is reported. Finally, efforts towards a novelsynthetic route to (?)-grandisol utilising the transannular Claisen rearrangementchemistry is described.Section three details the experimental procedures and spectroscopic data for thecompounds described in section two.
Date Issued
2009-06
Copyright Statement
Attribution NoDerivatives 4.0 International Licence (CC BY-ND)
Creator
Gore, Sophie
Publisher Institution
Imperial College London (University of London)
Qualification Level
Doctoral
Qualification Name
Doctor of Philosophy (PhD)