The hydroxyalkylation reactions of aceanthrenequinone (6) and acenapthenequinone (7) with a series of arenes have been studied. In reactions with the Bronsted superacid CF3SO3H (triflic acid), the condensation products are formed in good yields (58-99%, 10 examples) with high regioselectivity. Computational studies were also done to examine the structures and energies of mono- and diprotonated species from 6 and 7. The results from the condensation reactions are consistent with the formation of superelectrophilic species involving protosolvation of carboxonium ion intermediates. (c) 2007 Elsevier B.V. All rights reserved.