Herein we disclose the first report on the synthesis of oxindole derivatives from acetanilide via Ir(iii)-catalyzed intermolecular C-H functionalization with diazotized Meldrum's acid. A broad range of substituted anilides were found to react smoothly under the Ir(iii)-catalytic system to afford the corresponding N-protected oxindoles. The N-protecting groups, such as Ac, Bz or Piv, can be easily removed to furnish the oxindole. Various synthetic applications of the synthesized oxindole were also demonstrated.

Cp*Co(iii)-catalyzed C-H amidation of azobenzene with dioxazolones has been developed. The amidation reaction does not require external oxidants and gives carbon dioxide as the only by-product. Both symmetrical and unsymmetrical azobenzenes were found to undergo amidation smoothly with broad functional group tolerance.

A one‐pot synthesis of indole derivatives from readily available acetanilides and diazo compounds was developed. This IrIII‐catalyzed C–H alkylation and annulation reaction proceeds under mild conditions and generates molecular nitrogen and water as byproducts. Various types of synthetically versatile N‐substituted indoles, including N‐acetyl, N‐pivolyl, and N‐benzoyl indoles, were prepared.