Cationic Carbon-to-Nitrogen Rearrangements in N-(Arylsulfonoxy)amines

Article abstract of DOI:10.1021/jo00211a014

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.