TY - BOOK

T1 - The selective palladium-catalysed decarboxylative coupling of nucleophiles in the presence of propargylic electrophiles

AU - Kenny, Miles

PY - 2017

Y1 - 2017

N2 - This thesis describes the development of a palladium-catalysed chemo- andregioselective decarboxylative coupling of 1,3-dicarbonyl compounds andnitrogen nucleophiles in the presence of propargylic electrophiles.The first part of this thesis focuses on the palladium-catalysed cross-couplingreaction involving two 1,3-dicarbonyl compounds in a regio- andchemoselective manner via an allylic linker. The reaction is applied to a widerange of substrates and forms two C–C bonds and installs two all-carbonquaternary centres. Mechanistic studies to help deduce the mechanism of thereaction are described, which shows that by utilising a propargyl enolcarbonate as one of the coupling partners, the regioselectivity of this processcan be predictably controlled.The second part of this thesis focuses on the palladium-catalysed crosscouplingreaction of 1,3-dicarbonyl compounds with indole, pyrrole, imidazoleand pyrazole nucleophiles via an allylic linker. Despite the weakly acidicnature of N-heterocycles, the reaction proceeds with good efficiency, completeregio- and chemoselectivity and broad substrate scope. Mechanistic studieshave also been carried out to help deduce the mechanism of the reaction.The third part of this thesis centres around the development of the palladiumcatalysedcross-coupling reaction of two 1,3-dicarbonyl compounds in anenantioselective manner. Focus is given to the enantioselective alkenylationand enantioselective allylic alkylation reactions. Optimisation of the reactionconditions as well as the expansion of the substrate scope is described.Finally, a discussion of future work, comprehensive conclusions as well asexperimental procedures for the preparation of new compounds, backed up byfull analytical characterisation, are disclosed.

AB - This thesis describes the development of a palladium-catalysed chemo- andregioselective decarboxylative coupling of 1,3-dicarbonyl compounds andnitrogen nucleophiles in the presence of propargylic electrophiles.The first part of this thesis focuses on the palladium-catalysed cross-couplingreaction involving two 1,3-dicarbonyl compounds in a regio- andchemoselective manner via an allylic linker. The reaction is applied to a widerange of substrates and forms two C–C bonds and installs two all-carbonquaternary centres. Mechanistic studies to help deduce the mechanism of thereaction are described, which shows that by utilising a propargyl enolcarbonate as one of the coupling partners, the regioselectivity of this processcan be predictably controlled.The second part of this thesis focuses on the palladium-catalysed crosscouplingreaction of 1,3-dicarbonyl compounds with indole, pyrrole, imidazoleand pyrazole nucleophiles via an allylic linker. Despite the weakly acidicnature of N-heterocycles, the reaction proceeds with good efficiency, completeregio- and chemoselectivity and broad substrate scope. Mechanistic studieshave also been carried out to help deduce the mechanism of the reaction.The third part of this thesis centres around the development of the palladiumcatalysedcross-coupling reaction of two 1,3-dicarbonyl compounds in anenantioselective manner. Focus is given to the enantioselective alkenylationand enantioselective allylic alkylation reactions. Optimisation of the reactionconditions as well as the expansion of the substrate scope is described.Finally, a discussion of future work, comprehensive conclusions as well asexperimental procedures for the preparation of new compounds, backed up byfull analytical characterisation, are disclosed.

KW - palladium

KW - catalysed

KW - decarboxylative

U2 - 10.17635/lancaster/thesis/141

DO - 10.17635/lancaster/thesis/141

M3 - Doctoral Thesis

PB - Lancaster University

ER -