A remote carbonyl group up to six atoms away from the acetal group can induce 1,2-asymmetric induction in nucleophilic substitution reactions of acyclic acetals. Isolation of a cyclic carbonate under Lewis acidic conditions and computational studies suggested that the remote carbonyl group participated through the formation of a cyclic dioxocarbenium ion intermediate. The stereochemical outcomes depended on the size of the alkyl substituent and that of the nucleophile employed.