|dc.identifier.citation||Cornellà, J. 2012. Silver(I)-Mediated Decarboxylative Transformations; Benzoic Acids as Aryl Donors in Organic Synthesis. Queen Mary University of London.||en_US
|dc.description.abstract||The use of aromatic carboxylic acids as coupling agents in cross-coupling reactions
has arisen in the past few years as a very useful tool for organic chemists. The
generation of CO2 as the main byproduct has placed this novel approach amongst the
greenest alternatives to the traditional cross-couplings, where stoichiometric metal
salt waste is usually generated. This thesis contains the study of a novel
decarboxylative approach towards the synthesis of C–C bonds for the formation of
biaryl structures based on Ag(I) salts. The introduction contains an overview of the
recent developments that have appeared in the literature concerning this novel mode
of activation, and a discussion on how decarboxylative transformations have given
rise to powerful methodologies involving high atom and step economy.
This thesis starts describing the development of the first intermolecular
decarboxylative direct arylation protocol. Such methodology was applied to the direct
arylation of indoles using benzoic acids as coupling partners. This reaction proceeds
in a regioselective fashion giving exclusively the arylated product at the C3 position.
Moreover, the use of catalytic amounts of Ag(I) salts were found to efficiently
protodecarboxylate a wide range of benzoic acids bearing electron-withdrawing or
electron-donating groups at the ortho position. In addition, such protocol was applied
to heteroaromatic acids bearing α heteroatoms to the carboxylic acid.
(Hetero)aromatic carboxylic acids were also proven to be suitable candidates to
perform decarboxylative homocoupling to give good yields of the dimers.
Further to the Ag(I)-mediated decarboxylative methodologies, Au(I) salts were also
found to undergo decarboxylation of (hetero)aromatic carboxylic acids providing a
wide range of stable aryl-gold(I) compounds with excellent yields.
Finally, the first methodology for a meta-selective direct C–H arylation using
iodoarenes as coupling partners is also reported. This process, which is compatible
with a wide range of meta substituents, utilises carboxylic acids as traceless directing
groups affording complete control upon the regioselectivity of the direct C–H
|dc.publisher||Queen Mary University of London||en_US
|dc.title||Silver(I)-Mediated Decarboxylative Transformations; Benzoic Acids as Aryl Donors in Organic Synthesis.||en_US
|dc.rights.holder||The copyright of this thesis rests with the author and no quotation from it or information derived from it may be published without the prior written consent of the author||