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

by David Herrero Navarro
Doctoral thesis
Date of Examination:2024-12-10
Date of issue:2025-02-05
Advisor:Prof. Dr. Manuel Alcarazo
Referee:Prof. Dr. Manuel Alcarazo
Referee:Prof. Dr. Kai Tittmann
Referee:Prof. Dr. Ricardo A. Mata
Referee:Prof. Dr. Franc Meyer
Referee:Prof. Dr. Johannes C. L. Walker
Referee:Dr. Holm Frauendorf
Persistent Address: http://dx.doi.org/10.53846/goediss-11062

 

 

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Abstract

English

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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