A rhenium complex, [ReBr(CO)(3)(thf)](2), catalyzes the insertion of alpha,beta-unsaturated carboryl compounds into a C-H bond of aromatic compounds having nitrogen-containing directing groups. In this reaction, Re-2(CO)(10) call also be used as a catalyst. When imines are employed as the aromatic substrates, sequential cyclization proceeds and indene derivatives are obtained in good to excellent yields. This reactivity is ill contrast to those of ruthenium and rhodium complexes, which are usually used as catalysts in the insertion reactions of unsaturated molecules into a C-H bond. Investigations oil the reaction mechanism indicate that the rhenium catalyst promotes C-H bond activation of aromatic compounds, the insertion of alpha,beta-unsaturated carbonyl compounds into a Re-C bond, and intramolecular nucleophilic cyclization followed by reductive elimination and the elimination of an amine.