Cationic N-Heterocyclic Carbene Copper-Catalyzed [1,3]-Alkoxy Rearrangement of N-Alkoxyanilines

Abstract

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.