The interaction of 2-monosubstituted 1,3-dioxolanes with 3-hexyl-1-ethylaluminacyclopentane leads to the cleavage of the Al–C bond of the metallocycle and the formation of ethylene glycol monoethers after hydrolysis of the resulting reaction mixture. Catalytic amounts of ZrCl4 or Ni(acac)2 activate the process. The reaction of 2-monosubstituted 1,3-dioxolanes with 1-ethyl-3-naphthylaluminacyclopentane yields the product of cleavage of the exocyclic Al–Et bond of aluminacyclopentane.