O-(Alkoxycarbonyl)-N-arylhydroxylamines were efficiently converted to 2-aminophenol derivatives by cationic cobalt catalysts at 30 °C. The results of O-labeling experiments suggested that rearrangement of the alkoxycarbonyl group from the aniline nitrogen to the ortho position proceeded in an unprecedented [1,3] manner.
The [1,3]-alkoxy rearrangement reactions of N-alkoxyanilines were efficiently catalyzed by cationic N-heterocyclic carbene (NHC)-Cu catalysts in affording 2-alkoxyaniline derivatives in good to excellent yields with high functional group compatibility. For N-alkoxyanilines having an electron-withdrawing substituent at the meta-position, the alkoxy group selectively migrated to the more hindered ortho-position. In contrast, the alkoxy group migrated to the less hindered ortho-position for N-alkoxyanilines having an electron-donating substituent. Mechanistic studies suggest that the rearrangement reactions proceed via an intramolecular route.
Cu-catalyzed reaction between O-propargylic oximes and azodicarboxylates proceeded via 2,3-rearrangement followed by [4 + 2] cycloaddition, in which N-allenylnitrone acts as 2-azadiene.
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