New methods to synthesise sulfur-containing compounds
<p> In this thesis, novel methodologies towards the synthesis of a range of sulfur-containing compounds are documented. These compounds include sulfinamides, sulfonimidamides, sulfonimidoyl fluorides and a range of sulfonyl containing functional groups, for example, sulfones and sulfonamides....
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| Format: | Thesis |
| Language: | English |
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2021
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| _version_ | 1811141333401731072 |
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| author | Lo, PKT |
| author2 | Willis, M |
| author_facet | Willis, M Lo, PKT |
| author_sort | Lo, PKT |
| collection | OXFORD |
| description | <p> In this thesis, novel methodologies towards the synthesis of a range of sulfur-containing compounds are documented. These compounds include sulfinamides, sulfonimidamides, sulfonimidoyl fluorides and a range of sulfonyl containing functional groups, for example, sulfones and sulfonamides. These developed methods employ easy-to-handle sulfur dioxide surrogates, DABSO, and the sulfinylamine, TrNSO, exploiting nickel catalysis and organometallic reagents.</p>
<p>Chapter 1 provides an overview of the properties, applications and synthesis of sulfonyl-containing compounds and sulfonimidamides. An introduction to the use of sulfur dioxide in organic chemistry is given.</p>
<p>Chapter 2 describes the development of a new nickel-catalysed sulfination of (hetero)aryl boronic acids, using DABSO to synthesise aryl sulfinates in situ. The sulfinates are trapped using a range of electrophiles to form a variety of sulfonyl-containing compounds. This protocol tolerates an unprecedented range of electron-deficient and pharmaceutically relevant (hetero)aryl boronic acids, allowing the direct synthesis of active pharmaceutical ingredients (APIs).</p>
<p>Chapter 3 documents the preparation of sulfinamides using organometallic reagents and nitrogen-based nucleophiles in a streamlined one-pot, three-step procedure. Metal sulfinates, first generated from the addition of organometallic reagents to DABSO, are reacted with thionyl chloride to form sulfinyl chlorides as the key intermediates. Subsequently treating the sulfinyl chlorides with a range of nitrogen-nucleophiles delivers sulfinamides.</p>
<p>Chapter 4 presents the discovery of a new method to synthesise sulfinamides from aryl boroxines and sulfinylamine, TrNSO, through a nickel-catalysed protocol. The sulfinamides are further converted into sulfonimidamides, sulfonamides and sulfonimidoyl fluorides in a one-pot multi-step reaction sequence. Deprotection of the trityl-protected sulfinamide is also demonstrated to give the primary sulfinamide.</p>
<p>Chapter 5 summarises the research and presents potential future work.</p>
<p>Chapter 6 documents the experimental procedures and data.</p> |
| first_indexed | 2024-03-06T23:04:22Z |
| format | Thesis |
| id | oxford-uuid:63462b25-85a5-443e-b661-cb6a19d95343 |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-09-25T04:36:13Z |
| publishDate | 2021 |
| record_format | dspace |
| spelling | oxford-uuid:63462b25-85a5-443e-b661-cb6a19d953432024-09-24T07:19:40ZNew methods to synthesise sulfur-containing compoundsThesishttp://purl.org/coar/resource_type/c_db06uuid:63462b25-85a5-443e-b661-cb6a19d95343Chemistry, OrganicEnglishHyrax Deposit2021Lo, PKTWillis, M<p> In this thesis, novel methodologies towards the synthesis of a range of sulfur-containing compounds are documented. These compounds include sulfinamides, sulfonimidamides, sulfonimidoyl fluorides and a range of sulfonyl containing functional groups, for example, sulfones and sulfonamides. These developed methods employ easy-to-handle sulfur dioxide surrogates, DABSO, and the sulfinylamine, TrNSO, exploiting nickel catalysis and organometallic reagents.</p> <p>Chapter 1 provides an overview of the properties, applications and synthesis of sulfonyl-containing compounds and sulfonimidamides. An introduction to the use of sulfur dioxide in organic chemistry is given.</p> <p>Chapter 2 describes the development of a new nickel-catalysed sulfination of (hetero)aryl boronic acids, using DABSO to synthesise aryl sulfinates in situ. The sulfinates are trapped using a range of electrophiles to form a variety of sulfonyl-containing compounds. This protocol tolerates an unprecedented range of electron-deficient and pharmaceutically relevant (hetero)aryl boronic acids, allowing the direct synthesis of active pharmaceutical ingredients (APIs).</p> <p>Chapter 3 documents the preparation of sulfinamides using organometallic reagents and nitrogen-based nucleophiles in a streamlined one-pot, three-step procedure. Metal sulfinates, first generated from the addition of organometallic reagents to DABSO, are reacted with thionyl chloride to form sulfinyl chlorides as the key intermediates. Subsequently treating the sulfinyl chlorides with a range of nitrogen-nucleophiles delivers sulfinamides.</p> <p>Chapter 4 presents the discovery of a new method to synthesise sulfinamides from aryl boroxines and sulfinylamine, TrNSO, through a nickel-catalysed protocol. The sulfinamides are further converted into sulfonimidamides, sulfonamides and sulfonimidoyl fluorides in a one-pot multi-step reaction sequence. Deprotection of the trityl-protected sulfinamide is also demonstrated to give the primary sulfinamide.</p> <p>Chapter 5 summarises the research and presents potential future work.</p> <p>Chapter 6 documents the experimental procedures and data.</p> |
| spellingShingle | Chemistry, Organic Lo, PKT New methods to synthesise sulfur-containing compounds |
| title | New methods to synthesise sulfur-containing compounds |
| title_full | New methods to synthesise sulfur-containing compounds |
| title_fullStr | New methods to synthesise sulfur-containing compounds |
| title_full_unstemmed | New methods to synthesise sulfur-containing compounds |
| title_short | New methods to synthesise sulfur-containing compounds |
| title_sort | new methods to synthesise sulfur containing compounds |
| topic | Chemistry, Organic |
| work_keys_str_mv | AT lopkt newmethodstosynthesisesulfurcontainingcompounds |