ortho-Amino difunctionalization of aryl triflates has been achieved via a three-component reaction. The cascade reaction proceeds through a zincate base-mediated deprotonative formation of a reactive aryne intermediate, in situ nucleophilic addition, and coupling with electrophilic partners. This strategy leverages the advantageous reactivity of organozincate intermediates, enabling the installation of various functionalities such as amine, azide, oxygen, sulfur, halide, alkynyl, aryl, vinyl, and alkyl groups in a modular manner for the synthesis of diverse aniline skeletons.