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Title: Sigmatropic rearrangement-metathesis based approaches to cyclopentadienes
Author: Coulson, Bethan
ISNI:       0000 0004 7232 6667
Awarding Body: Imperial College London
Current Institution: Imperial College London
Date of Award: 2018
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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.
Supervisor: Craig, Donald Sponsor: Commonwealth Scientific and Industrial Research Organization (Australia)
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral