80953-41-9Relevant academic research and scientific papers
Structural Effects on the Transition States of Imine-Forming Eliminations in N-Substituted O-(Arylsulfonyl)hydroxylamines
Hoffman, Robert V.,Shankweiler, Jean M.
, p. 4019 - 4022 (2007/10/02)
A series of amines with various alkyl and aryl substituents at C-1 were converted to the corresponding N-(arylsulfonoxy)amines, which served as precursors for base-promoted, imine-forming elimination.By varying the bases used to promote the elimination and by varying the leaving groups attached to nitrogen, the Broensted parameters β and βlgCH3 were determined.These were used to locate the transition state on the More O'Ferrall-Jencks energy surface for elimination.Substituents were found to influence the structure of the activated complex markedly.Resonance effects were most important, while inductive effects had little influence .
Cationic Carbon-to-Nitrogen Rearrangements in N-(Arylsulfonoxy)amines
Hoffman, Robert V.,Kumar, Anil
, p. 1859 - 1863 (2007/10/02)
A series of N-alkyl-O-(arylsulfonyl)hydroxylamines was prepared by the reaction of amines with bis(arylsulfonyl)peroxides.In the absence of base, these amine derivatives underwent rearrangement involving the migration of groups from carbon to nitrogen.The migratory tendencies of the groups which rearranged were found to be in the order Ph>H>alkyl>Me.The migratory aptitudes Ph/Me>72 and n-hexyl/Me=4.2 suggest that these rearrangements are polar in nature and involve electron-deficient nitrogen species.Furthermore the migration of groups was found to be sensitive to the substitution pattern at the migration origin and subject to stereoelectronic control.
