Synthesis of meta-Aminophenol Derivatives via Cu-Catalyzed [1,3]-Rearrangement-Oxa-Michael Addition Cascade Reactions

Cu-catalyzed reactions of N-alkoxy-2-methylanilines and alcohols in the presence of catalytic amounts of IPrCuBr and AgSbF₆ afforded the corresponding meta-aminophenol derivatives in good to high yields. These reactions proceed via a [1,3]-rearrangement, in which the alkoxy group migrates from the nitrogen atom to the methyl-substituted ortho position, followed by an oxa-Michael reaction of the resulting ortho-quinol imine intermediate.