Electrochemically induced fluoride umpolung

Electrophilic fluorinating agents typically possess a N-F bond, itself typically forged by the action of extremely hazardous fluorine gas at a nitrogen centre. It will be tested whether anodic oxidation of various amines can generate aminium radicals or dications capable of reacting with in situ fluoride ions to form the desired N-F bond. Candidate amines will first be screened by examining at the DFT level of theory the thermodynamics of one- and two-electron oxidations of selected amine systems and subsequent N-F bond formation, as well as calculating electronic distributions of the oxidised species. Promising candidates will then be synthesised and subjected to cyclic voltammetric and chronoamperometric measurements to gather empirical data such as oxidation potentials to compare with theoretical values, as well as to aid in the determination of possible electrochemical reaction outcomes in the presence of fluoride. If N-F bonds are furnished in the desired electrochemical fashion, it is hoped that the methodology can be applied to [18F]fluoride ions to conveniently generate 18F-labelled fluorinating agents.