Anodic Functionalisation of Alkenes Catalysed by Diselenids

• Applicants: Professor Dr. Alexander Breder; Professorin Dr. Inke Siewert
• Subject Area: Organic Molecular Chemistry - Synthesis and Characterisation ; Inorganic Molecular Chemistry - Synthesis and Characterisation
• Term: since 2020
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 433320673

The project aims to develop a synthetic method for the electrochemically driven and selenium-catalyzed fluorination and amination of non-activated alkenes and its application in natural product synthesis. Fluorination reactions of carbon skeletons play a crucial role for example in the synthesis of pharmaceuticals, theranostics or agrochemicals. Fluorine atoms in such agents may i.a. increase the metabolic stability and bioavailability, modify protein-ligand interactions, or can be harnessed in drug-targeting. Not least because of these reasons, there is an immense demand for efficient protocols that allow for the facile construction of fluorinated compounds. In addition to fluorinations, also amination reactions play a fundamental role in organic synthesis, as the C–N bond is one of the most prominent structural motifs found in organic compounds. Carbon–nitrogen bonds are of relevance to various scientific disciplines such as biology (e.g., peptide and proteins), pharmaceutics (e.g., drug design), or material sciences (e.g., polyamide fibres and tissues). Against this backdrop, the continuing demand for the development of efficient and sustainable protocols for the assembly of C−N bonds becomes strikingly apparent. To particularly address the issues of atom and redox-economy, the goal of this research is the anodic oxidation alkenes catalysed by diselenides as a key step for the construction of C–F and C–N bonds. By avoiding the use of customary chemical oxidants as well as pre-oxidized building blocks for the incorporation of fluorine and nitrogen residues (e.g., via nucleophilic substitution), the concept proposed herein represents a sustainable alternative to most of concurrent methods. Furthermore, electrochemistry can be exploited in versatile methods to generate and analyse reactive species under mild conditions, which can lead on the hand to higher chemoselectivities and on the other hand to an improved mechanistic understanding of the reactions in question.

• DFG Programme: Research Grants