Regiodivergent nucleophilic fluorination under hydrogen bonding phase transfer catalysis
<p><b>Chapter 1</b> briefly introduces the different concepts that have been applied in regioselective catalysis. Non-catalyst controlled and catalyst-controlled methods for inducing regioselectivity are presented. Despite the abundance of fluorination methods, no catalytic regiodi...
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| Format: | Thesis |
| Language: | English |
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2021
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| _version_ | 1826315652787339264 |
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| author | Afratis, K |
| author2 | Gouverneur, V |
| author_facet | Gouverneur, V Afratis, K |
| author_sort | Afratis, K |
| collection | OXFORD |
| description | <p><b>Chapter 1</b> briefly introduces the different concepts that have been applied in regioselective catalysis. Non-catalyst controlled and catalyst-controlled methods for inducing regioselectivity are presented. Despite the abundance of fluorination methods, no catalytic regiodivergent nucleophilic fluorination has been recorded in literature to the best of our knowledge. The potential of hydrogen bonding phase transfer catalysis (HBPTC) is then discussed as a viable method to address this problem. Finally, the aim of this thesis is summarised.</p>
<p><b>Chapter 2</b> focuses on the efforts taken towards the development of a novel hydrogen bonding-mediated regioselective nucleophilic fluorination. The effect of hydrogen bond donor (HBD) urea organocatalysts on altering fluoride’s anion kinetic preference is demonstrated. It is also presented that HBD urea organocatalysts are capable of not only changing the kinetic regiochemical preference of fluoride, but also induce a thermodynamic product equilibration. First, this chapter focuses on the substrate of choice and then expands on the development and optimisation of a kinetically and thermodynamically controlled regiodivergent nucleophilic fluorination protocol. </p>
<p><b>Chapter 3</b> presents the scope of the urea-catalysed regioselective fluorination. Substrate synthesis and the efforts made to expand the synthetic applicability of the developed methodology are also presented. </p>
<p><b>Chapter 4</b> describes our attempts towards merging our developed catalytic regioselective fluorination with a kinetic resolution process and presents proof of concept for a novel regiodivergent parallel kinetic resolution.</p>
<p><b>Chapter 5</b> gives full experimental procedures and characterisation data for all novel compounds.</p> |
| first_indexed | 2024-03-07T07:22:07Z |
| format | Thesis |
| id | oxford-uuid:1069ba14-5640-42d4-abec-459e32f03a78 |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-12-09T03:30:01Z |
| publishDate | 2021 |
| record_format | dspace |
| spelling | oxford-uuid:1069ba14-5640-42d4-abec-459e32f03a782024-12-01T13:22:35ZRegiodivergent nucleophilic fluorination under hydrogen bonding phase transfer catalysisThesishttp://purl.org/coar/resource_type/c_db06uuid:1069ba14-5640-42d4-abec-459e32f03a78Chemistry, OrganicPhase-transfer catalysisEnglishHyrax Deposit2021Afratis, KGouverneur, V<p><b>Chapter 1</b> briefly introduces the different concepts that have been applied in regioselective catalysis. Non-catalyst controlled and catalyst-controlled methods for inducing regioselectivity are presented. Despite the abundance of fluorination methods, no catalytic regiodivergent nucleophilic fluorination has been recorded in literature to the best of our knowledge. The potential of hydrogen bonding phase transfer catalysis (HBPTC) is then discussed as a viable method to address this problem. Finally, the aim of this thesis is summarised.</p> <p><b>Chapter 2</b> focuses on the efforts taken towards the development of a novel hydrogen bonding-mediated regioselective nucleophilic fluorination. The effect of hydrogen bond donor (HBD) urea organocatalysts on altering fluoride’s anion kinetic preference is demonstrated. It is also presented that HBD urea organocatalysts are capable of not only changing the kinetic regiochemical preference of fluoride, but also induce a thermodynamic product equilibration. First, this chapter focuses on the substrate of choice and then expands on the development and optimisation of a kinetically and thermodynamically controlled regiodivergent nucleophilic fluorination protocol. </p> <p><b>Chapter 3</b> presents the scope of the urea-catalysed regioselective fluorination. Substrate synthesis and the efforts made to expand the synthetic applicability of the developed methodology are also presented. </p> <p><b>Chapter 4</b> describes our attempts towards merging our developed catalytic regioselective fluorination with a kinetic resolution process and presents proof of concept for a novel regiodivergent parallel kinetic resolution.</p> <p><b>Chapter 5</b> gives full experimental procedures and characterisation data for all novel compounds.</p> |
| spellingShingle | Chemistry, Organic Phase-transfer catalysis Afratis, K Regiodivergent nucleophilic fluorination under hydrogen bonding phase transfer catalysis |
| title | Regiodivergent nucleophilic fluorination under hydrogen bonding phase transfer catalysis |
| title_full | Regiodivergent nucleophilic fluorination under hydrogen bonding phase transfer catalysis |
| title_fullStr | Regiodivergent nucleophilic fluorination under hydrogen bonding phase transfer catalysis |
| title_full_unstemmed | Regiodivergent nucleophilic fluorination under hydrogen bonding phase transfer catalysis |
| title_short | Regiodivergent nucleophilic fluorination under hydrogen bonding phase transfer catalysis |
| title_sort | regiodivergent nucleophilic fluorination under hydrogen bonding phase transfer catalysis |
| topic | Chemistry, Organic Phase-transfer catalysis |
| work_keys_str_mv | AT afratisk regiodivergentnucleophilicfluorinationunderhydrogenbondingphasetransfercatalysis |