A mild, general, and convenient palladium-catalyzed direct arylation of the 5-position of azoles with aryl bromides, efficiently promoted by tetrabutylammonium acetate, is described. 1-Methylpyrazole, oxazole, and thiazole reacted at 70 degrees C in N,N-dimethylacetamide by using Pd(OAc)(2) as the catalyst precursor. Electron-poor and -rich functional groups, including the free hydroxy group, are well tolerated in the electrophilic partner. A variety of 5-aryl-1-methylimidazoles were also very efficiently obtained simply by raising the reaction temperature to 110 degrees C. This ligand-free protocol was successfully applied to the one-pot synthesis of two bioactive natural compounds, balsoxin and texaline, starting from oxazole by sequential direct arylation of the 5- and 2-positions.