Sigmatropic rearrangement – metathesis based approaches to cyclopentadienes
File(s)
Author(s)
Coulson, Bethan
Type
Thesis
Abstract
This thesis is divided into four chapters.
Chapter one is a review of cyclopentadienes (Cps), and is split by sub-classification of applications in organometallics, applications in organic methodology, synthesis of complex Cps from post carbocycle modification and de novo synthesis of Cp.
Chapter two introduces the decarboxylative Claisen rearrangement (dCr) and details investigations of the application of this reaction towards Cp synthesis using three different activating groups.
Chapter three focuses on the decarboxylative Claisen rearrangement (dCr) from a computational aspect. It begins with a brief review of the mechanism of the [3,3]-sigmatropic rearrangement and examples of density functional theory (DFT) to rationalise Ireland-Claisen rearrangements. The kinetic data of [3,3]-sigmatropic rearrangement of tosyl malonates is studied and compared to DFT calculations. The method devised is tested on literature dCr reactions and then used predictively to interpret synthetic outcomes.
Chapter four provides experimental procedures and characterisation data.
Chapter one is a review of cyclopentadienes (Cps), and is split by sub-classification of applications in organometallics, applications in organic methodology, synthesis of complex Cps from post carbocycle modification and de novo synthesis of Cp.
Chapter two introduces the decarboxylative Claisen rearrangement (dCr) and details investigations of the application of this reaction towards Cp synthesis using three different activating groups.
Chapter three focuses on the decarboxylative Claisen rearrangement (dCr) from a computational aspect. It begins with a brief review of the mechanism of the [3,3]-sigmatropic rearrangement and examples of density functional theory (DFT) to rationalise Ireland-Claisen rearrangements. The kinetic data of [3,3]-sigmatropic rearrangement of tosyl malonates is studied and compared to DFT calculations. The method devised is tested on literature dCr reactions and then used predictively to interpret synthetic outcomes.
Chapter four provides experimental procedures and characterisation data.
Version
Open Access
Date Issued
2017-10
Date Awarded
2018-03
Copyright Statement
Attribution NoDerivatives 4.0 International Licence (CC BY-ND)
Advisor
Craig, Donald
Sponsor
Commonwealth Scientific and Industrial Research Organization (Australia)
Publisher Department
Chemistry
Publisher Institution
Imperial College London
Qualification Level
Doctoral
Qualification Name
Doctor of Philosophy (PhD)