The dual behaviour of acyl azides in transition-metal-catalyzed direct CÀH amidation is investigated. Variously substituted acyl azides reacted smoothly with 7-azaindoles providing a diversity of CÀC or CÀN 7-azaindole amidated derivatives. This amidation reaction shows an excellent controllability, which is believed to be dependent on catalyst system.

Rhodium(iii)-catalyzed N-directed ortho C-H activation and subsequent roll-over C-H activation represents an important strategy to synthesize fused polycyclic compounds. Herein, the novel methodology broadens the scope of the coupling partner to alkenes, which working smoothly with 7-azaindoles has been proven to be an efficient and atom-economical strategy to access complex π-conjugated 7-azaindole derivatives.

An efficient rhodium-catalyzed dehydrogenative Heck-type reaction between N-aryl-substituted 7-azaindoles and various alkenes through a H -releasing process without the need of any oxidizing agent was developed. The novel methodology broadens the scope of metal-catalyzed hydrogen-releasing reactions to include rhodium catalysis.

A convenient rhodium(III)-catalyzed cascade reaction of 7-azaindoles and alkynes through multiple C-H bond activation for the synthesis of unique [5]azahelicenes has been developed. The optical property of these screw-shaped helicene derivatives could be further utilized in electronic devices to recognize mercury ions.