A facile synthetic method for preparing 3-amino-2-silylaryl triflates via regioselective silylamination of 3-(triflyloxy)arynes with N-silylamines is described. Fluoride-mediated generation of 3-aminobenzyne from 3-amino-2-silylphenyl triflate, easily prepared by this method, in the presence of various arynophiles efficiently afforded diverse aniline derivatives, including a 5-aminocoumarin derivative, demonstrating the utility of aryne relay approach.