ABSTRACT
Aromatic nucleophilic photosubstitution reactions can be viewed as an important alternative to aromatic functionalizations promoted by catalysis with metal complexes. This chapter reviews nucleophilic photosubstitution reactions with attention to the possible synthetic significance. An important part of the intramolecular nucleophilic photosubstitutions concerns the photo-Smiles rearrangements. The presence of a methoxy group, a good leaving group in nucleophilic substitution reactions, in position 2 did not alter the course of the reaction, in contrast of the meta-directing effect by the nitro group on photosubstitution reactions observed in nitroanisoles and nitroveratroles. Most of the work concerning the formation of aryl-nitrogen bond in photosubstitution reactions has been based on the use of amines as nucleophiles. Imidazole used as model nucleophile in similar experiments was able to replace both the nitro and the fluoro group, with a preference for the former one, leading to the formation of an aryl-nitrogen bond.
