Intramolecular and intermolecular alkylations of carbocation precursors of limited ionization ability, principally N, O-acetals, without the use of an exogenous reagent have been developed. The reactions are carried out in 1, 1, 2, 2-tetrachloroethane (TCE) and take advantage of the ability of this solvent to continuously release small amounts of HCl by thermolytic elimination. A study of the reaction led to several improved protocols such as ( ...