Transketalizations and acetonations of 2,2-dimethoxypropane and 2-methoxypropene, respectively, using 1,2,3-propane and 1,2,4-butanetriol have been carried out, at room temperatue, under the mediation of the following butyltin chlorides: BuSnCl(3), Bu(2)SnCl(2), Bu(3)SnCl, (Bu(2)SnCl)(2)O and BuSn(OH)(2)Cl. The main products are represented by 1,3-dioxolane derivatives when the four mediators are employed. When BuSn(OH)(2)Cl is employed, particularly in the case of acetonation, a mixture of dioxolane derivatives together with two acetone ketals containing 1,2-O-isopropylidenetriol residues is obtained.