Applications of DABSO for the delivery of sulfur dioxide in organic synthesis
<p>This thesis documents the development of novel synthetic methodologies for the incorporation of sulfur dioxide into organic molecules employing the amine-sulfur dioxide complex DABSO (<em>vide infra</em>). These developed processes serve to access a range of sulfonyl-containing...
| Main Author: | |
|---|---|
| Other Authors: | |
| Format: | Thesis |
| Language: | English |
| Published: |
2015
|
| Subjects: |
| _version_ | 1826290960302080000 |
|---|---|
| author | Deeming, A |
| author2 | Willis, M |
| author_facet | Willis, M Deeming, A |
| author_sort | Deeming, A |
| collection | OXFORD |
| description | <p>This thesis documents the development of novel synthetic methodologies for the incorporation of sulfur dioxide into organic molecules employing the amine-sulfur dioxide complex DABSO (<em>vide infra</em>). These developed processes serve to access a range of sulfonyl-containing (-SO<sub>2</sub>-) compounds including sulfones and sulfonamides, <em>via</em> sulfinic acid precursors.</p> <p><b>Chapter 1</b> provides an overview of the synthesis and applications of sulfonyl-containing compounds and the organic chemistry of sulfur dioxide. A comprehensive introduction to the developed uses of sulfur dioxide surrogates in organic chemistry is given. The synthetic utility of metal sulfinates towards accessing sulfonyl-containing compounds is also discussed.</p> <p><b>Chapter 2</b> details the development of a one-pot sulfone synthesis <em>via</em> metal sulfinates generated from organometallic reagents and DABSO. Alkyl, alkenyl and (hetero)aryl sulfinates prepared from organolithium and Grignard reagents can be efficiently coupled with a range of electrophiles to access a range of products including diaryl, aryl-heteroaryl and β-hydroxy sulfones.</p> <p><b>Chapter 3</b> describes an array-compatible, one-pot sulfonamide synthesis employing metal sulfinates and <em>N</em>-chloroamines as <em>in situ</em>-generated intermediates. This employs DABSO and sodium hypochlorite (bleach) as simple reagents and organolithium, organozinc and Grignard reagents along with amines as readily-accessible building blocks. The robust nature of this methodology and its potential application in discovery chemistry is demonstrated with a 65-compound array synthesis.</p> <p><b>Chapter 4</b> documents the development of a palladium-catalysed sulfination reaction of boronic acids to access a range of sulfonyl-containing compounds. This involved the establishment of a one-pot/one step synthesis of sulfones leading to the discovery of a redox-neutral, ligand-free sulfination procedure using DABSO and palladium(II) catalysis. Sulfinic acid derivatives can be generated and subsequently trapped <em>in situ</em> with a variety of electrophiles to furnish sulfones and sulfonamides.</p> <p><b>Chapter 5</b> summarises the research and the potential future work.</p> <p><b>Chapter 6</b> provides experimental details and data.</p> |
| first_indexed | 2024-03-07T02:52:11Z |
| format | Thesis |
| id | oxford-uuid:ae0a6c5c-57a1-48bc-b219-ad22678d51ca |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-07T02:52:11Z |
| publishDate | 2015 |
| record_format | dspace |
| spelling | oxford-uuid:ae0a6c5c-57a1-48bc-b219-ad22678d51ca2022-03-27T03:40:05ZApplications of DABSO for the delivery of sulfur dioxide in organic synthesisThesishttp://purl.org/coar/resource_type/c_db06uuid:ae0a6c5c-57a1-48bc-b219-ad22678d51caOrganic synthesisEnglishOxford University Research Archive - Valet2015Deeming, AWillis, M<p>This thesis documents the development of novel synthetic methodologies for the incorporation of sulfur dioxide into organic molecules employing the amine-sulfur dioxide complex DABSO (<em>vide infra</em>). These developed processes serve to access a range of sulfonyl-containing (-SO<sub>2</sub>-) compounds including sulfones and sulfonamides, <em>via</em> sulfinic acid precursors.</p> <p><b>Chapter 1</b> provides an overview of the synthesis and applications of sulfonyl-containing compounds and the organic chemistry of sulfur dioxide. A comprehensive introduction to the developed uses of sulfur dioxide surrogates in organic chemistry is given. The synthetic utility of metal sulfinates towards accessing sulfonyl-containing compounds is also discussed.</p> <p><b>Chapter 2</b> details the development of a one-pot sulfone synthesis <em>via</em> metal sulfinates generated from organometallic reagents and DABSO. Alkyl, alkenyl and (hetero)aryl sulfinates prepared from organolithium and Grignard reagents can be efficiently coupled with a range of electrophiles to access a range of products including diaryl, aryl-heteroaryl and β-hydroxy sulfones.</p> <p><b>Chapter 3</b> describes an array-compatible, one-pot sulfonamide synthesis employing metal sulfinates and <em>N</em>-chloroamines as <em>in situ</em>-generated intermediates. This employs DABSO and sodium hypochlorite (bleach) as simple reagents and organolithium, organozinc and Grignard reagents along with amines as readily-accessible building blocks. The robust nature of this methodology and its potential application in discovery chemistry is demonstrated with a 65-compound array synthesis.</p> <p><b>Chapter 4</b> documents the development of a palladium-catalysed sulfination reaction of boronic acids to access a range of sulfonyl-containing compounds. This involved the establishment of a one-pot/one step synthesis of sulfones leading to the discovery of a redox-neutral, ligand-free sulfination procedure using DABSO and palladium(II) catalysis. Sulfinic acid derivatives can be generated and subsequently trapped <em>in situ</em> with a variety of electrophiles to furnish sulfones and sulfonamides.</p> <p><b>Chapter 5</b> summarises the research and the potential future work.</p> <p><b>Chapter 6</b> provides experimental details and data.</p> |
| spellingShingle | Organic synthesis Deeming, A Applications of DABSO for the delivery of sulfur dioxide in organic synthesis |
| title | Applications of DABSO for the delivery of sulfur dioxide in organic synthesis |
| title_full | Applications of DABSO for the delivery of sulfur dioxide in organic synthesis |
| title_fullStr | Applications of DABSO for the delivery of sulfur dioxide in organic synthesis |
| title_full_unstemmed | Applications of DABSO for the delivery of sulfur dioxide in organic synthesis |
| title_short | Applications of DABSO for the delivery of sulfur dioxide in organic synthesis |
| title_sort | applications of dabso for the delivery of sulfur dioxide in organic synthesis |
| topic | Organic synthesis |
| work_keys_str_mv | AT deeminga applicationsofdabsoforthedeliveryofsulfurdioxideinorganicsynthesis |