No abstract

A tandem approach to (hetero)arene‐fused benzo[f]imidazo[1,2‐d][1,4]oxazepines has been described which involves condensation of bis‐nucleophilic 2‐(2‐hydrohyaryl)imidazoles with reactivity‐matched o‐dihalo and o‐halonitro (hetero)aromatic substrates. The process is generally regioselective with respect to the unsymmetrically substituted imidazole ring and proceeds via two SNAr events (intermolecular first and then intramolecular) intermitted by a Smiles rearrangement. In some cases, the last SNAr step provides a rare example of nucleophilic displacement of a nitro group or a halogen in non‐activated positions of a (hetero)aromatic ring which does not require the use of a metal catalyst.