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  • 2017kennyphd

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The selective palladium-catalysed decarboxylative coupling of nucleophiles in the presence of propargylic electrophiles

Research output: ThesisDoctoral Thesis

Published
Publication date2017
Number of pages352
QualificationPhD
Awarding Institution
Supervisors/Advisors
Publisher
  • Lancaster University
Original languageEnglish

Abstract

This thesis describes the development of a palladium-catalysed chemo- and
regioselective decarboxylative coupling of 1,3-dicarbonyl compounds and
nitrogen nucleophiles in the presence of propargylic electrophiles.
The first part of this thesis focuses on the palladium-catalysed cross-coupling
reaction involving two 1,3-dicarbonyl compounds in a regio- and
chemoselective manner via an allylic linker. The reaction is applied to a wide
range of substrates and forms two C–C bonds and installs two all-carbon
quaternary centres. Mechanistic studies to help deduce the mechanism of the
reaction are described, which shows that by utilising a propargyl enol
carbonate as one of the coupling partners, the regioselectivity of this process
can be predictably controlled.
The second part of this thesis focuses on the palladium-catalysed crosscoupling
reaction of 1,3-dicarbonyl compounds with indole, pyrrole, imidazole
and pyrazole nucleophiles via an allylic linker. Despite the weakly acidic
nature of N-heterocycles, the reaction proceeds with good efficiency, complete
regio- and chemoselectivity and broad substrate scope. Mechanistic studies
have also been carried out to help deduce the mechanism of the reaction.
The third part of this thesis centres around the development of the palladiumcatalysed
cross-coupling reaction of two 1,3-dicarbonyl compounds in an
enantioselective manner. Focus is given to the enantioselective alkenylation
and enantioselective allylic alkylation reactions. Optimisation of the reaction
conditions as well as the expansion of the substrate scope is described.
Finally, a discussion of future work, comprehensive conclusions as well as
experimental procedures for the preparation of new compounds, backed up by
full analytical characterisation, are disclosed.