A operationally simple synthesis of (Z)-1,2-dihydro-2-iminoquinolines that proceeds under mild conditions is achieved by copper-catalyzed reaction of 1-(2-aminophenyl)ethan-1-ones, sulfonyl azides and terminal ynones. In particular, the reaction goes through a base-free CuAAC/ring-opening process to obtain the Z-configured products due to hydrogen bonding.