Alkylation of epoxides can be effected with trialkylaluminum/water system, which is much superior to the parent trialkylalnminum. Bidentate bis(dialkyl)aluminoxanes and their hypothetical analogues seem to be active species for the double activation of epoxy substrates. Such double-activation ability is emphasized using several synthetic examples in comparison with the corresponding monodentate derivatives. The double coordination complex formation of bidentate (Me2Al)(2)O is characterized with THF by H-1 and C-13 NMR spectroscopy. (C) 1999 Elsevier Science Ltd. All rights reserved.