New methods for the synthesis of sulfur functional groups

<p>Sulfur(VI) functionalities exhibit promising properties for both pharmaceutical and agrochemical applications. Described in this thesis are new methodologies for the synthesis of a range of S(VI) containing compounds, including sulfonimidamides, sulfondiimidoyl fluorides, and sulfondiimidoa...

Ausführliche Beschreibung

Bibliographische Detailangaben
1. Verfasser: Ding, M
Weitere Verfasser: Willis, MC
Format: Abschlussarbeit
Sprache:English
Veröffentlicht: 2023
Schlagworte:
Beschreibung
Zusammenfassung:<p>Sulfur(VI) functionalities exhibit promising properties for both pharmaceutical and agrochemical applications. Described in this thesis are new methodologies for the synthesis of a range of S(VI) containing compounds, including sulfonimidamides, sulfondiimidoyl fluorides, and sulfondiimidoates. The developed methods exploit sulfinylamine reagents as synthetic linchpins, using organometallic reagents and amines/alcohols as key building blocks, that provide rapid and modular access to these demanding aza-sulfur scaffolds.</p> <br> <p><strong>Chapter 1</strong> is a review introducing sulfur(VI) functional groups, with a focus on the current synthetic methods for accessing sulfonimidamides, sulfondiimidoyl fluorides, and sulfondiimidoates. The properties and applications of these compounds are also considered.</p> <br> <p><strong>Chapter 2</strong> details the discovery of several novel <em>N</em>-silyl sulfinylamines. Notably, a stable sulfinylamine reagent, <em>N</em>-sulfinyltriisopropylsilylamine (TIPS-NSO), enables rapid preparation of primary sulfinamides. A hypervalent iodine-mediated amination of these primary sulfinamides then delivers a diverse range of sulfonimidamides, including a medicinally relevant sulfonimidamide-derivative.</p> <br> <p><strong>Chapter 3</strong> describes the development of a practical synthesis of sulfondiimidoyl fluorides. The route employs organometallic reagents and pre-generated sulfurdiimides as starting materials, proceeding <em>via</em> sulfinamidines, and generating sulfondiimidoyl fluorides with broad structural variation. Divergent syntheses of sulfondiimines and sulfondiimidamides through subsequent SuFEx (sulfur-fluoride exchange) reactions are achieved.</p> <br> <p><strong>Chapter 4</strong> documents a two-step synthetic approach towards sulfondiimidoates, using organometallic reagents, a sulfurdiimide reagent, and alcohols as key components. An iodine(III)-mediated oxidative reaction of primary sulfinamidines directly forms sulfondiimidoates. Variation of the nitrogen substituents of sulfondiimidoates through controlled manipulation is well-tolerated, allowing for the preparation of a series of <em>N</em>-functionalised derivatives.</p> <br> <p><strong>Chapter 5</strong> summaries the research and discusses potential areas for future work.</p> <br> <p><strong>Chapter 6</strong> provides experimental procedures and data for this research.</p>