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Title: The decarboxylative Ireland-Claisen rearrangement : methodology studies and approaches to the total synthesis of (-)-suaveoline
Author: Lewis, Simon Eliot
ISNI:       0000 0001 3609 1328
Awarding Body: Imperial College London
Current Institution: Imperial College London
Date of Award: 2006
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This thesis is divided into three sections. Section one is a review of recent progress in the synthesis of macroline, sarpagine and ajmaline-related indole alkaloids. The review covers approximately the last ten years of published literature. Section two is divided into two parts and discusses the results of research into the decarboxylative Ireland-Claisen rearrangement. Part one gives the background to the project and discusses the mechanism of this rearrangement. The development of methodology for the synthesis of bifunctional rearrangement substrates is detailed. The competitive rearrangement of these bifunctional substrates is outlined and trends in reactivity are discussed. An account is given of the application of the decarboxylative Ireland-Claisen rearrangement to a cyclic malonate, which gave rise to a cyclopropane. Efforts towards a cyclic malonate substrate are detailed, including the use of carbon suboxide. Part two concerns studies towards the total synthesis of (-)-suaveoline. The retrosynthetic analysis is explained and pertinent methodology introduced. The initial construction of a synthetically relevant rearrangement substrate is outlined. The reasons for the failure of this substrate to rearrange are discussed, as is the modified protecting group strategy that was adopted. Subsequent successful rearrangement and the synthesis of a key cyclopentenyl intermediate are described. Unsuccessful attempts to alkylate this cyclopentene are detailed and an alternative strategy is put forward. Novel methodology for the formation of pyridine-A/-oxides is disclosed and attempts to apply this to the synthesis of suaveoline are discussed. Section three is the experimental section, which gives detailed descriptions of the synthesis and spectroscopic characteristics of the compounds discussed in section two.
Supervisor: Craig, Donald ; Lansdell, Mark Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral