On the chemistry of sulfur: Development of NOS bridge model systems and Stereoretentive 2,3-bis(trifluoromethyl)cyclopropanation of heteroarenes via sulfonium salts

von David Herrero Navarro
Dissertation
Datum der mündl. Prüfung:2024-12-10
Erschienen:2025-02-05
Betreuer:Prof. Dr. Manuel Alcarazo
Gutachter:Prof. Dr. Manuel Alcarazo
Gutachter:Prof. Dr. Kai Tittmann
Gutachter:Prof. Dr. Ricardo A. Mata
Gutachter:Prof. Dr. Franc Meyer
Gutachter:Prof. Dr. Johannes C. L. Walker
Gutachter:Dr. Holm Frauendorf
Zum Verlinken/Zitieren: http://dx.doi.org/10.53846/goediss-11062

 

 

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Englisch

This thesis presents research conducted across two distinct projects in sulfur chemistry. The first project focused on the synthesis of model systems based on biphenyl, xanthene, and triazamacrocyclic scaffolds to investigate the highly relevant NOS bridge. This novel crosslink, identified in proteins in 2021 by our collaborators in the research group of Prof. Dr. Kai Tittmann, consists of a thiol and an amine linked via an oxygen atom. The second project led to the development of a novel sulfonium salt transfer reagent incorporating a 2,3-bis(trifluoromethyl)cyclopropane moiety. Alongside the synthesis of this reagent, alkylation reactions were explored using two distinct methodologies: photocatalytic conditions and cesium carbonate (Cs₂CO₃) as a base. This enabled the late-stage functionalisation of pharmaceutically relevant heterocycles such and quinoxalinones and imidazoles, granting access to the underexplored 2,3-bis(trifluoromethyl)cyclopropane moiety.
Keywords: Sulfonium salts; NOS bridge; Cyclopropanation; Trifluoromethyl group; Late-stage functionalisation; Photocatalysis; Radical chemistry; Thiol oxidation
 
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