Developing a Catalytic Strategy to Address Regiocontrol in Radical Reactions of Aromatic Heterocycles

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Construction of basic heteroarenes with varied substitution patterns is of great importance, but direct transformation of heterocyclic C-H bonds is a major challenge, often due to incompatibility with metal catalysts. Minisci-type additions are radical addition processes in which a basic heterocycle is protonated with a concomitant lowering of its LUMO, before attack by 'nucleophilic' radicals. This is a deceptively simple method with no catalyst required. The problem that has held back its widespread use is a lack of regioselectivity on heterocycles such as pyridines and quinolines due to insufficiently different LUMO coefficients of the C2 and C4 positions. We will develop a catalytic approach to Minisci additions that will allow us to control regioselectivity between C2 and C4. We anticipate that successful realisation of this strategy will allow the wealth of radical chemistry to be applied to valuable basic heterocycles with new-found regiocontrol.