An iodine‐promoted one‐pot cascade oxidative annulation reaction has been developed for the synthesis of [1,2,3]triazolo[1,5‐a]quinolines from methyl azaarenes and N‐tosylhydrazines. The reaction has a broad substrate scope and can be easily scaled up to gram‐scale. 1,2,3‐Triazoles are an important skeletal structure for the construction of C−C and C−P bonds, 2‐cyclopropylquinolines and imidazo[1,5‐a]quinolines, for which different synthetic applications were explored.

Hydrogenation of imines [(I) and (III)] is accomplished using an environmentally benign process in the reversible CO2—H2O system where water is thought to be the terminal hydrogen source.

An oxidative [3+1+1] convergent domino cyclization is disclosed. This protocol enables to get quinoline, quinoxaline, quinazolin‐4(3H)‐one and benzo[d]thiazole attached 2,4,5‐trisubstituted oxazoles from methyl azaarenes, benzoins, and NH4OAc in the presence of iodine and molecular sieves without any metal catalyst. The reaction features wide substrate scope, good functional group tolerance, mild reaction conditions, and easily available substrates.