Diastereoselective\nSubstitution Reactions of Acyclic\nAcetals Controlled by Remote Participation of an Acyloxy Group

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