We have developed a protocol for efficient synthesis of N-aryl-substituted azacycles from aryl amines and cyclic ethers using I₂/NaH₂PO₂ as the mediator. A diverse range of aryl amines and cyclic ethers undergo amination reaction to generate products in good to excellent yields with good functional group tolerance. This reaction can be easily scaled up to give N-aryl-substituted azacycles on a gram scale. Further chemical manipulation of the products enabled useful transformations of the quinoline ring, including bromination and acetylation.