Abstract
The investigation of photoredox‐induced intra‐ and intermolecular radical [4+2] annulations of indoles confronted us with a puzzling dichotomous behavior of structurally closely related intermediate 3‐indolyl radicals, which either undergo exclusive oxidation to tricyclic tetrahydropyridoindoles or reduction to benzindolizidine products under identical reaction conditions. A combined experimental and computational study revealed that only very subtle structural changes in the substrate–reactant complexes of the key radical intermediates with amine radical cations steer the divergent product selectivities, instead of the usual reactivity parameters such as ionization potentials or partial charges.
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