Synthesis of novel cycloperoxides

Simple item page
dc.check.chapterOfThesis10 year embargoen
dc.check.date2033-12-31
dc.contributor.advisorO'Sullivan, Tim
dc.contributor.authorHennessy, Mary C.en
dc.contributor.funderIrish Research Councilen
dc.date.accessioned2023-10-06T10:30:52Z
dc.date.available2023-10-06T10:30:52Z
dc.date.issued2023
dc.date.submitted2023
dc.descriptionControlled Accessen
dc.description.abstractCycloperoxides represent an important class of compounds for synthetic chemists. Their asymmetric synthesis will be the focus of this thesis, specifically using organocatalysis. Chapter 1 contains a review of organocatalysed peroxidations from the literature and within the research group to date. The key aims and objectives of this project are also outlined. Chapter 2 describes the generation of a diverse library of trans-γ,δ-unsaturated β-keto esters. The preparation of these compounds involves both Wittig chemistry and Lewis acid-catalysed C-H insertion strategies. The synthesis of a cis-γ,δ-unsaturated β-keto ester and a non-enolisable α,α-disubstituted β-keto ester are also outlined. The optimisation of the organocatalysed peroxidation of γ,δ-unsaturated β-keto esters in terms of enantioselectivity and yields is described in Chapter 3. To determine the enantioselectivity of the peroxidation reaction, a robust chiral HPLC methodology is required. The development of a suitable separation methodology is outlined in this chapter. Chapter 4 describes a novel synthetic route to 3,5-substituted 1,2-dioxolane ethyl esters through the chemoselective reduction of a δ-peroxy-β-keto ester to the corresponding δ-peroxy-β-hydroxy ester, and subsequent phosphorus pentoxide-mediated cyclisation. Chapter 5 outlines our preparation of several novel 1,2-dioxolane carboxylic acids and various attempts at subsequently introducing an N-acyl sulfonamide to the 1,2-dioxolane core. Chapter 6 details the main conclusions of this work and proposes several avenues of research to investigate in future. Chapter 7 contains all relevant experimental procedures, including spectroscopic and analytical data.en
dc.description.statusNot peer revieweden
dc.description.versionAccepted Versionen
dc.format.mimetypeapplication/pdfen
dc.identifier.citationHennessy, M. C. 2023. Synthesis of novel cycloperoxides. PhD Thesis, University College Cork.
dc.identifier.endpage359
dc.identifier.urihttps://hdl.handle.net/10468/15075
dc.language.isoenen
dc.publisherUniversity College Corken
dc.relation.projectIrish Research Council (Grant no. GOIPG/2018/496)
dc.rights© 2023, Mary Constance Hennessy.
dc.rights.urihttps://creativecommons.org/licenses/by-nc-nd/4.0/
dc.subjectCycloperoxidesen
dc.subjectPeroxidationen
dc.subject1,2-Dioxolaneen
dc.subjectCyclisationen
dc.subjectγ,δ-unsaturated β-keto estersen
dc.subjectAsymmetric synthesisen
dc.subjectOrganocatalysisen
dc.titleSynthesis of novel cycloperoxides
dc.typeDoctoral thesisen
dc.type.qualificationlevelDoctoralen
dc.type.qualificationnamePhD - Doctor of Philosophyen
Files
Original bundle
Now showing 1 - 3 of 3
Thumbnail Image
Name:
HennessyMC_PhD2023.docx
Size:
6.33 MB
Format:
Microsoft Word XML
Description:
Full Text E-thesis (Word)
Thumbnail Image
Name:
HennessyMC_PhD2023.pdf
Size:
8.21 MB
Format:
Adobe Portable Document Format
Description:
Full Text E-thesis
Thumbnail Image
Name:
Submission for Examination Form
Size:
406.65 KB
Format:
Adobe Portable Document Format
License bundle
Now showing 1 - 1 of 1
Thumbnail Image
Name:
license.txt
Size:
5.2 KB
Format:
Item-specific license agreed upon to submission
Description:
Download
Collections
Research Theses
Analytical & Biological Chemistry Research Facility - Doctoral Theses
Chemistry - Doctoral Theses
College of Science, Engineering and Food Science - Doctoral Theses