The nucleophilic alkyl radicals generated from the RAE demonstrated exceptional scope, with tertiary, secondary, and primary radicals successfully coupling with 3-fluorocyanopyridine with a wide functional group tolerance (Fig. ). Only the methyl radical proving to be too high energy to fragment and hence unreactive. As expected, tertiary alkyl radicals proved the most successful due to their nucleophilicity and stability, providing a straightforward route to highly hindered quaternary carbon centres, common in many natural and biologically active products. The reaction showed tolerance to various functional groups, including ketones, aryl groups, alkenes, alcohols, and esters. Pharmaceutically relevant motifs, such as cyclic ethers and protected amines, were also retained making this protocol particularly suitable for latestage functionalisation of complex substrates.