The PIFA/NaCl combination was found effective in the chlorination of aromatic compounds. Unlike protocols employing diaryliodonium salts, a new discovered method for the α-arylation of the activated ketones is discribed.The β-ketoesters, β-diketones and α-cyanoketones were all suitable substrates for this process. Best yields are obtained using cyclic cyanoketones, and the reaction can be carried out on a multigram scale. In addition, a range of substituted iodoarylbis(trifluoroacetates) have been prepared and applied to the synthesis of the more highly substituted arylketones.