Studies in iridium and manganese catalysis in C-H activation and reductive transformations

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dc.check.chapterOfThesisThe full thesis is under an embargo for a period of 3 years. As such during this designated 3-year period, the final thesis may not be viewed or downloaded on CORA.en
dc.check.date2028-05-31
dc.contributor.advisorMcglacken, Gerard P.
dc.contributor.authorCourtney, Eimearen
dc.contributor.funderIrish Research Councilen
dc.contributor.funderHigher Education Authorityen
dc.date.accessioned2025-02-18T09:52:14Z
dc.date.available2025-02-18T09:52:14Z
dc.date.issued2024
dc.date.submitted2024
dc.description.abstractHeteroaromatic compounds are fundamental building blocks in pharmaceutical, agrochemical and material chemistry. The efficient and selective derivatisation of heteroarenes is a critical tool for organic synthesis. C−H activation has emerged as an effective means to access diversified heteroaromatic motifs. In particular, iridium-catalysed C−H borylation has proven a useful means of heteroarene functionalisation, due to its ability to produce highly versatile aryl organoboronate intermediates. The quinoline nucleus is a ubiquitous, strategic target, given its role as a key scaffold in a plethora of synthetic and naturally occurring pharmacologically active compounds. Chapter 1 showcases a robust one-pot protocol which enables rapid late-stage functionalisation of this important class of pharmacophores. Chapter 1, Part I describes the direct borylation and transformation of the C-7 position of 6-fluoroquinolones in excellent yields. This protocol is further expanded upon in Chapter 1, Part II to include the borylation of the biologically significant N-ethyl 3-carboxylate-6-fluoroquinolone in good yields. Furthermore, we have identified a tuneable reactivity applicable to the N-substituted 3-carboxylate-6-fluoroquinolone motif, which can be controlled through judicious choice, and equivalents, of borylating agent employed. In recent years, earth-abundant 3d transition metal catalysts, such as manganese, have gained popularity as alternatives to expensive precious metals. This trend stems from the urgent need to develop new, efficient, and sustainable green methodologies. The use of readily available metals, instead of rare noble metals, is a key focus in green chemistry. Chapter 2 of this thesis explores the synthesis of various carbonyl manganese phosphine complexes and their applications in C–H activation. Chapter 2, Part I details the synthesis and characterisation of three carbonyl manganese phosphine complexes through spectroscopic methods and investigates their role in C–H activation reactions. Additionally, the formation of corresponding manganacycle complexes was studied to understand the fate of the ligand during the catalytic cycle. Chapter 2, Part II describes the preparation of a polymer-bound phosphine manganese complex from commercially available sources via a straightforward one-step process. This catalyst has shown broad applicability and promising results in protocols such as C–H activation, (de)hydrogenation, and hydrofunctionalisation, yielding valuable products ranging from chemical feedstocks to complex heteroaromatic motifs in moderate to good yields.en
dc.description.statusNot peer revieweden
dc.description.versionAccepted Versionen
dc.format.mimetypeapplication/pdfen
dc.identifier.citationCourtney, E. 2024. Studies in iridium and manganese catalysis in C-H activation and reductive transformations. PhD Thesis, University College Cork.
dc.identifier.endpage315
dc.identifier.urihttps://hdl.handle.net/10468/17055
dc.language.isoenen
dc.publisherUniversity College Corken
dc.rights© 2024, Eimear Courtney.
dc.rights.urihttps://creativecommons.org/licenses/by-nc-nd/4.0/
dc.subjectChemistry
dc.subjectOrganic synthesis
dc.subjectCatalysis
dc.subjectManganese
dc.subjectIridium
dc.subjectBorylation
dc.subjectFluoroquinolones
dc.titleStudies in iridium and manganese catalysis in C-H activation and reductive transformations
dc.typeDoctoral thesisen
dc.type.qualificationlevelDoctoralen
dc.type.qualificationnamePhD - Doctor of Philosophyen
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