The reaction of arynes, generated from ortho-(trimethylsilyl) aryl triflates, with the CO bond of formamides gave salicylaldehyde derivatives via the formation of formal [2+ 2] adducts. The sequential transformation of arynes into ortho-disubstituted arenes, o-aminoalkylphenols or o-hydroxyalkylphenols, was achieved by one-pot procedure using dialkylzincs.