title: β-Elimination of an Aziridine to an Allylic Amine: A Mechanistic Study.
abstract: The base-induced rearrangement of aziridines has been examined using a combination of calculations and experiment. The calculations show that the substituent on nitrogen is a critical feature that greatly affects the favorability of both α-deprotonation, and β-elimination to form an allylic amine. Experiments were carried out to determine whether E2-like rearrangement to the allylic amine with lithium diisopropyl amide (LDA) is possible. N-Tosyl aziridines were found to deprotonate on the tosyl group, preventing further reaction. A variety of N-benzenesulfonyl aziridines having both α- and β-protons decomposed when treated with LDA in either tetrahydrofuran or hexamethylphosphoramide. However, when α-protons were not present, allylic amine was formed, presumably via β-elimination.
authors.affiliation: Department of Chemistry, Xavier University of Louisiana, 1 Drexel Drive, New Orleans LA 70125, USA.
authors.forename: Kathleen M
authors.initials: KM
authors.lastname: Morgan
authors.forename: Garry
authors.initials: G
authors.lastname: Brown
authors.forename: Monique A
authors.initials: MA
authors.lastname: Pichon
authors.forename: Geannette Y
authors.initials: GY
authors.lastname: Green