New reactions of 2-methyleneaziridines
Mumford, Peter Marten (2009) New reactions of 2-methyleneaziridines. PhD thesis, University of Warwick.
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Official URL: http://webcat.warwick.ac.uk/record=b2317886~S9
Chapter One reviews the synthesis, properties and reactions of 2-methyleneaziridines, the subject of this thesis.
Chapter Two describes the use of these heterocycles in the development of a new four-component synthesis of biologically important α-aminophosphonates. This new chemistry proceeds in moderate to good yield via a “one-pot” process that involves the sequential formation of three new intermolecular bonds and a quaternary carbon centre. This reaction is tolerant to a range of functionalities incorporated in the various components. Deprotection of one of these α-aminophosphonates to the corresponding α-aminophosphonic acid is achieved via a two-step process in very good yield.
Chapter Three discusses efforts made towards the development of a multi-component imino Diels-Alder reaction for the generation of 2,3-dihydro-4-pyridones. Initial work suggests acyclic ketimine intermediates are unsuitable for this process.
Chapter Four reports unsuccessful attempts made to generate
methyleneaziridines bearing electron-withdrawing substituents via in situ N-derivatisation.
In Chapter Five, the synthesis of 1,1-disubstituted tetrahydro-β-carbolines from methyleneaziridines is described. The reaction is shown to proceed in moderate to very good yields and a range of β-carbolines were successfully synthesised. High levels of diastereocontrol are demonstrated using a substrate containing a pre-existing stereocentre.
Chapter Six details the experimental procedures and characterisation data for the novel compounds produced.
|Item Type:||Thesis or Dissertation (PhD)|
|Subjects:||T Technology > TP Chemical technology
Q Science > QD Chemistry
|Library of Congress Subject Headings (LCSH):||Aziridines -- Research, Heterocyclic compounds -- Research, Chemical reactions -- Research, Carbolines -- Research|
|Official Date:||June 2009|
|Institution:||University of Warwick|
|Theses Department:||Department of Chemistry|
|Supervisor(s)/Advisor:||Shipman, Mike ; Tarver, Gary|
|Sponsors:||Biotechnology and Biological Sciences Research Council (Great Britain) (BBSRC) ; Schering-Plough Corporation (SPC)|
|Format of File:|
|Extent:||196 leaves : ill., charts|
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