The novel 1,6-amino addition reaction to the naphthalene ring system followed by the electrophilic alkylation is presented. The detailed mechanistic studies suggest the existence of two equilibrations that result in the 1,4-amino addition reaction and the 1,6-amino addition reaction. The stability and bulkiness of lithium amide play a key role in directing the course of the reaction. The transformation of the 1,6-amino adducts to other useful compounds is concisely demonstrated. The methodology provides a remote-controlled diastereoselective synthesis of δ-amino acid derivatives.