A general method has been developed for in situ trapping of arylmetal intermediates by halogen, sulfur, ketone, and aldehyde electrophiles affording the functionalization of the most acidic position in arene. Pentafluorobenzene, benzothiazole, and benzoxazole can be functionalized by using K(3)PO(4) base. For less acidic arenes, tBuOLi base is required. Arenes with DMSO pK(a) values of 35 or less are reactive.