To accomplish the proposed one-pot reaction we intended to utilize reactive aryne intermediates as arene electrophiles for achieving a metal-free C(sp2)-O and -Ncoupling. For the initial aryne-mediated arylation of o-iodophenols 3, preliminary investigations revealed a procedure using CsF in MeCN as the most effective coupling strategy with (trimethylsilyl)aryl triflates 4 as aryne precursors to obtain diphenylether scaffolds 5