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β‐Elimination of an aziridine to an allylic amine: a mechanistic study
Author(s) -
Morgan Kathleen M.,
Brown Garry,
Pichon Monique A.,
Green Geannette Y.
Publication year - 2011
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.1838
Subject(s) - chemistry , allylic rearrangement , deprotonation , tosyl , amine gas treating , substituent , medicinal chemistry , amide , aziridine , nucleophile , organic chemistry , ring (chemistry) , catalysis , ion
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. Copyright © 2011 John Wiley & Sons, Ltd.