Some adamantyl-stabilised reactive intermediates
File(s)
Author(s)
O'Reilly, Daniel
Type
Thesis
Abstract
The first preparative example and crystallographic characterisation of a 2-tert- alkyldioxolan-2-ylium ion salt (111) is reported herein. Oxonium ion 111 was found to be the end-point of a novel diastereoconvergent system – the first example of this behaviour in oxonium ions of any type – and was formed as the final product in hydride abstraction of either of diasteromeric dioxolanes 100 and 101 and in the halide abstraction of either of diastereomeric bromohydrin ester 123 and 124 (Ch 1). Evidence indirectly supporting an intermediate bromocyclopropanone in the thermal rearrangements of bromoallene oxides is presented (Ch 2).
Version
Open Access
Date Issued
2022-02
Date Awarded
2022-07
Copyright Statement
Creative Commons Attribution NonCommercial Licence
License URL
Advisor
Braddock, David
Sponsor
Engineering and Physical Sciences Research Council
Publisher Department
Chemistry
Publisher Institution
Imperial College London
Qualification Level
Doctoral
Qualification Name
Doctor of Philosophy (PhD)