Electrochemical processes to generate alkyl radicals

Radical chemistry is a cornerstone of organic synthesis, yet many radical techniques rely on reagents that are toxic or that generate significant quantities of waste. In this project we will work towards developing methods that can produce carbon-centred radicals from readily available carboxylic acid precursors, using only photons and electrons as reagents, and producing minimal by-products. The researcher will be working under the supervision of Prof Mike Porter. Recent research in the Porter group has shown that electrochemical reduction of a trifluoroacetyl pyridinium salt leads to the formation of a trifluoroacetyl radical; this can decarbonylate – i.e. lose carbon monoxide – to give a trifluoromethyl radical. The trifluoromethyl radical can then be used to functionalise an organic substrate. In this project, we aim to optimise and develop this methodology to produce a broad range of radicals from carboxylic acids, and to explore their subsequent reactivity. In parallel with developing a reductive method for radical production, we will also explore oxidative methods; in particular we hope to use a combination of electrochemistry and photochemistry to allow us to oxidise carboxylate salts to carboxy radicals, which can decarboxylate to generate the desired alkyl radicals. The project is ideally suited to a student with a strong interest in the development of organic synthetic methodology. No experience of electrochemistry is required.