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Synthesis and chemistry of methyleneaziridines bearing aryl groups
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Bayliffe, Frances (2013) Synthesis and chemistry of methyleneaziridines bearing aryl groups. PhD thesis, University of Warwick.
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Official URL: http://webcat.warwick.ac.uk/record=b2691372~S1
Abstract
This thesis describes the synthesis of methyleneaziridines bearing aryl groups and
investigates some of their chemistry, focusing on thermal rearrangements and
metal catalysed reactions. The inclusion of an N-aryl group is desirable as it is
thought it might facilitate new types of reactions to be developed for use in
organic synthesis.
In chapter one, the synthesis of methyleneaziridines with N-EWGs and N-aryl
groups is investigated. Starting by exploring the possibility of using coppercatalysed
nitrene cyclisation, a common method for the synthesis of aziridines, the
synthesis of N-tosyl and N-troc methyleneaziridines was attempted. This led into
the synthesis of N-mesityl methyleneaziridine which was achieved in 85% yield
by ring closure of N-(2-iodopro-2-en-1-yl)-2,4,6-trimethylaniline using sodium
amide in ammonia. The effect of the leaving group (Br vs I) on the relative rates
of such ring closure reactions was explored and it was established that iodides
cyclise at a higher rate.
Chapter two describes the thermal rearrangement of N-mesityl
methyleneaziridines. A kinetic study was conducted to show the increased
propensity for N-mesityl methyleneaziridine to rearrange to the cyclopropylimine,
compared to N-alkyl methyleneaziridines. The application of this rearrangement
for the preparation of cyclopropylamines was explored.
Chapter three looks at metal-catalysed reactions of methyleneaziridines. It was
shown that N-mesityl methyleneaziridine will participate in a palladium-catalysed
reaction. Carbonylation reaction of methyleneaziridines, as reported by Alper1 and
Pauson-Khand reactions were also explored. A novel methyleneaziridine
containing cobalt/alkyne complex was produced in 40% yield.
Item Type: | Thesis (PhD) | ||||
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Subjects: | Q Science > QD Chemistry | ||||
Library of Congress Subject Headings (LCSH): | Aziridines -- Synthesis, Carbenes (Methylene compounds) -- Synthesis, Chemical reactions | ||||
Official Date: | June 2013 | ||||
Dates: |
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Institution: | University of Warwick | ||||
Theses Department: | Department of Chemistry | ||||
Thesis Type: | PhD | ||||
Publication Status: | Unpublished | ||||
Supervisor(s)/Advisor: | Shipman, Michael; Steven, Alan | ||||
Sponsors: | University of Warwick; Engineering and Physical Sciences Research Council (EPSRC); AstraZeneca (Firm) | ||||
Extent: | 173 leaves : illustrations. | ||||
Language: | eng |
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