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.
The base-induced rearrangement of aziridines has been exn class="Chemical">amined 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: Franklin A. Davis; Hu Liu; Chang-Hsing Liang; G. Venkat Reddy; Yulian Zhang; Tianan Fang; Donald D. Titus Journal: J Org Chem Date: 1999-11-26 Impact factor: 4.354
Authors: Kathleen M Morgan; Jamie A Ellis; Joseph Lee; Ashley Fulton; Shavonda L Wilson; Patrick S Dupart; Rosanna Dastoori Journal: J Org Chem Date: 2013-04-22 Impact factor: 4.354