UCSF

Nitroarenes are readily accessible bulk chemicals and can serve as versatile starting materials for a series of synthetic reactions. However, due to the inertness of the C_Ar-NO₂ bond, the direct denitrative substitution reaction with unactivated nitroarenes remains challenging. Chemists rely on sequential reduction and diazotization followed by the Sandmeyer reaction or the nucleophilic aromatic substitution of activated nitroarenes to realize nitro group transformations. Here we develop a general denitrative chlorination reaction under visible-light irradiation, in which the chlorine radical replaces the nitro moiety through the cleavage of the C_Ar-NO₂ bond. This practical method works with a wide range of unactivated nitro(hetero)arenes and nitroalkenes, is not sensitive to air or moisture and can proceed smoothly on a decagram scale. This transformation differs fundamentally from previous nucleophilic aromatic substitution reactions under thermal conditions in both synthesis and mechanism. Density functional theory calculations reveal the possible pathway for the substitution reaction.