I. Discovery and development of nickel-catalyzed 1,2-dicarbofunctionalization reactions of alkenes II. Synthesis and reactivity of nucleophilic calcium fluoride complexes with oxygenic ligand frameworks
<p><em>Part I. Discovery and Development of Nickel-Catalyzed 1,2-Dicarbofunctionalization Reactions of Alkenes.</p></em> <p>While much success has been achieved in the realm of 1,2-dicarbofunctionalization of alkenes under nickel catalysis, yet there remains a paucity...
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| Format: | Thesis |
| Language: | English |
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2024
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| _version_ | 1824458863046295552 |
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| author | Apolinar, O |
| author2 | Aldridge, S |
| author_facet | Aldridge, S Apolinar, O |
| author_sort | Apolinar, O |
| collection | OXFORD |
| description | <p><em>Part I. Discovery and Development of Nickel-Catalyzed 1,2-Dicarbofunctionalization Reactions of Alkenes.</p></em>
<p>While much success has been achieved in the realm of 1,2-dicarbofunctionalization of alkenes under nickel catalysis, yet there remains a paucity in using weak directing groups, dicarbofunctionalizing multisubstituted alkenes, and implementing asymmetric variants. In our investigations, we developed a method where we can leverage weak ketone native directing groups for the 1,2-diarylation of unactivated alkenes with excellent regioselectivity. Additionally, we serendipitously discovered that sulfonamides are uniquely effective in directing 1,2- dicarbofunctionalization of unactivated alkenes including 1,2-disubstituted and trisubstituted alkenes. In light of these findings, we demonstrate an enantioselective variant which was plausible by tuning the steric bulk of the sulfonamide directing group and finding the adequate flexibility of a chiral N,N-ligand.</p>
<p><em>Part II. Synthesis and Reactivity of Nucleophilic Calcium Fluoride Complexes with Oxygenic Ligand Frameworks.</p></em>
<p>The inorganic salt CaF2 is insoluble in water and in organic solvents making it difficult to study in situ. While efforts have been made in the solid state, solution state investigations would greatly shed more light into the nature of the nucleophilicity of the Ca–F bond. The majority of the known soluble, well-defined, calcium fluoride complexes are typically stabilized by amido-type ligands, and with only one ligand archetype showing fluoride delivery capabilities. We sought to investigate O-donor ligand scaffolds that may also stabilize calcium fluoride complexes and improve fluoride anion delivery compared to the amido-supported counterpart. In our investigations, we found that the TACN ligand was appropriate owing to its macrocyclic design, which encapsulates calcium. However, a novel desymmetrizing method of a (TACN)Ca complex had to be developed which allowed leeway for the synthesis of various dinuclear calcium mono- and difluoride complexes. Fluoride anion delivery upon electrophiles was found to be enhanced when compared to the notorious NON ligand framework.</p> |
| first_indexed | 2025-02-19T04:32:39Z |
| format | Thesis |
| id | oxford-uuid:17e4eaab-b226-4bce-b6f9-96eedc1ff3f2 |
| institution | University of Oxford |
| language | English |
| last_indexed | 2025-02-19T04:32:39Z |
| publishDate | 2024 |
| record_format | dspace |
| spelling | oxford-uuid:17e4eaab-b226-4bce-b6f9-96eedc1ff3f22025-01-15T07:51:09ZI. Discovery and development of nickel-catalyzed 1,2-dicarbofunctionalization reactions of alkenes II. Synthesis and reactivity of nucleophilic calcium fluoride complexes with oxygenic ligand frameworksThesishttp://purl.org/coar/resource_type/c_db06uuid:17e4eaab-b226-4bce-b6f9-96eedc1ff3f2CatalysisOrganic chemistryInorganic chemistryEnglishHyrax Deposit2024Apolinar, OAldridge, SEngle, KGouverneur, V<p><em>Part I. Discovery and Development of Nickel-Catalyzed 1,2-Dicarbofunctionalization Reactions of Alkenes.</p></em> <p>While much success has been achieved in the realm of 1,2-dicarbofunctionalization of alkenes under nickel catalysis, yet there remains a paucity in using weak directing groups, dicarbofunctionalizing multisubstituted alkenes, and implementing asymmetric variants. In our investigations, we developed a method where we can leverage weak ketone native directing groups for the 1,2-diarylation of unactivated alkenes with excellent regioselectivity. Additionally, we serendipitously discovered that sulfonamides are uniquely effective in directing 1,2- dicarbofunctionalization of unactivated alkenes including 1,2-disubstituted and trisubstituted alkenes. In light of these findings, we demonstrate an enantioselective variant which was plausible by tuning the steric bulk of the sulfonamide directing group and finding the adequate flexibility of a chiral N,N-ligand.</p> <p><em>Part II. Synthesis and Reactivity of Nucleophilic Calcium Fluoride Complexes with Oxygenic Ligand Frameworks.</p></em> <p>The inorganic salt CaF2 is insoluble in water and in organic solvents making it difficult to study in situ. While efforts have been made in the solid state, solution state investigations would greatly shed more light into the nature of the nucleophilicity of the Ca–F bond. The majority of the known soluble, well-defined, calcium fluoride complexes are typically stabilized by amido-type ligands, and with only one ligand archetype showing fluoride delivery capabilities. We sought to investigate O-donor ligand scaffolds that may also stabilize calcium fluoride complexes and improve fluoride anion delivery compared to the amido-supported counterpart. In our investigations, we found that the TACN ligand was appropriate owing to its macrocyclic design, which encapsulates calcium. However, a novel desymmetrizing method of a (TACN)Ca complex had to be developed which allowed leeway for the synthesis of various dinuclear calcium mono- and difluoride complexes. Fluoride anion delivery upon electrophiles was found to be enhanced when compared to the notorious NON ligand framework.</p> |
| spellingShingle | Catalysis Organic chemistry Inorganic chemistry Apolinar, O I. Discovery and development of nickel-catalyzed 1,2-dicarbofunctionalization reactions of alkenes II. Synthesis and reactivity of nucleophilic calcium fluoride complexes with oxygenic ligand frameworks |
| title | I. Discovery and development of nickel-catalyzed 1,2-dicarbofunctionalization
reactions of alkenes II. Synthesis and reactivity of nucleophilic calcium fluoride complexes with
oxygenic ligand frameworks |
| title_full | I. Discovery and development of nickel-catalyzed 1,2-dicarbofunctionalization
reactions of alkenes II. Synthesis and reactivity of nucleophilic calcium fluoride complexes with
oxygenic ligand frameworks |
| title_fullStr | I. Discovery and development of nickel-catalyzed 1,2-dicarbofunctionalization
reactions of alkenes II. Synthesis and reactivity of nucleophilic calcium fluoride complexes with
oxygenic ligand frameworks |
| title_full_unstemmed | I. Discovery and development of nickel-catalyzed 1,2-dicarbofunctionalization
reactions of alkenes II. Synthesis and reactivity of nucleophilic calcium fluoride complexes with
oxygenic ligand frameworks |
| title_short | I. Discovery and development of nickel-catalyzed 1,2-dicarbofunctionalization
reactions of alkenes II. Synthesis and reactivity of nucleophilic calcium fluoride complexes with
oxygenic ligand frameworks |
| title_sort | i discovery and development of nickel catalyzed 1 2 dicarbofunctionalization reactions of alkenes ii synthesis and reactivity of nucleophilic calcium fluoride complexes with oxygenic ligand frameworks |
| topic | Catalysis Organic chemistry Inorganic chemistry |
| work_keys_str_mv | AT apolinaro idiscoveryanddevelopmentofnickelcatalyzed12dicarbofunctionalizationreactionsofalkenesiisynthesisandreactivityofnucleophiliccalciumfluoridecomplexeswithoxygenicligandframeworks |