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dc.contributor.advisorSmith, Andrew David
dc.contributor.authorMunday, Elizabeth Sarah
dc.coverage.spatialxiii, 175 p.en_US
dc.description.abstractThis thesis details the development of enantioselective, isothiourea-catalysed, acyl-transfer methodology for the synthesis of atropisomers. Chapter 1 aims to introduce organocatalysis in the context of the current state-of-the art in Lewis base catalysis and its application in enantioselective acyl transfer. Following this, the importance of axial chirality and the current art in the synthesis of biaryl and non-biaryl atropisomers is introduced. The potential for isothiourea catalysis to provide a new platform in this area is then outlined. Chapter 2 outlines development of methodology for the acylative desymmetrisation of biaryl phenols. After optimisation of the desymmetrisation of a model system, computational and experimental techniques were used to probe the selectivity and mechanism of the process. The methodology was then extended to a scope of 14 biaryl substrates, providing highly enantioenriched products (up to 98:2 er, 54% isolated yield). Discussion of the mechanism of their formation, and the enantioselectivity of the process is also provided. Chapter 3 outlines attempts to extend the methodology developed in chapter 2 to the synthesis of molecules with a C–N stereogenic axis. The synthesis of several target biaryl heterocycle substrates was attempted and tentative attempts to adapt current acyl transfer methodology to these species is described. Additionally, the synthesis of atropisomeric anilides via N-acylation of secondary anilines is detailed. Chapter 4 contains a summary of the work that has been carried out for this thesis and the potential extensions to future work within the field of Lewis base organocatalysis. Chapter 5 provides the experimental details for the synthesis of the compounds which are contained in this thesis, as well as the associated analytical data for their characterisation.en_US
dc.description.sponsorship"This work was supported by the Engineering and Physical Sciences Research Council and EPSRC Centre for Doctoral Training in Critical Resource Catalysis [grant number EP/L016419/1]." -- Fundingen
dc.publisherUniversity of St Andrews
dc.relationData underpinning Elizabeth Sarah Munday's thesis. Munday, E.S., University of St Andrews. DOI:
dc.subject.lcshEnantioselective catalysisen
dc.titleCatalytic enantioselective acyl transfer for the synthesis of atropisomersen_US
dc.contributor.sponsorEngineering and Physical Sciences Research Council (EPSRC)en_US
dc.contributor.sponsorCritical Resource Catalysis Centre for Doctoral Training (CRITICAT)en_US
dc.type.qualificationnamePhD Doctor of Philosophyen_US
dc.publisher.institutionThe University of St Andrewsen_US
dc.rights.embargoreasonThesis restricted in accordance with University regulations. Print and electronic copy restricted until 10th February 2022en

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