An efficient and mild protocol for the direct conversion of arene C−H bonds to C−NH 2 without the need for extra deprotection step has been established, and to the best of our knowledge, this is the first time that the synthesis of primary anilines via nickel-mediated C(sp 2 )-H activations has been reported. This approach utilizes 8-aminoquinoline as the directing group and sodium azide, a cheap and commercially available material, as the nitrogen source. In addition, the reaction is highly selective, affording the mono-ortho-aminated benzam...