Rediscovery of a Broad Array of Lewis Acids for Living Cationic Polymerization in the Presence of an Added Base

Cationic polymerization of isobutyl vinyl ether using various metal halides was examined in toluene in the presence of an added base at $0^{\circ}C$. In conjunction with an appropriate weak base such as ethyl acetate or 1,4-dioxane, all metal halides but $FeBr_{3}\;and\;GaCl_{3}$ led to living cationic polymerization. The polymerization rates varied as follows: $FeBr_{3},\;GaCl_{3}\;>\;FeCl_{3}\;>\;SnCl_{4}\;>\;InCl_{3}\;>\;ZnCl_{2}\;>>\;AlCl_{3},\;HfCl_{4},\;ZrCl_{4}\;>\;EtAlCl_{2},\;BiCl_{3},\;TiCl4\;>>\;SiCl_{4}\;>\;GeCl_{4}$. This order partially corresponds to that of the equilibrium constant in the formation of a carbocation from a chloroalkane in the presence of a carbonyl compound. With extremely active Lewis acids, such as $FeBr_{3}\;and\;GaCl_{3}$, the use of a stronger base, THF, was required to achieve living polymerization.