Palladium-Catalyzed Synthesis of N-Cyclohexyl Anilines from Phenols with Hydrazine or Hydroxylamine via N-N/O Cleavage

Direct access to amines from biomass-based phenols via deoxygenative transformation remains greatly challenging in organic synthesis. Herein, we present a palladium-catalyzed deoxygenative amination of phenols (and their benzyl ether) with hydrazine as nitrogen source. The hydroxylamine/formic acid can be substituted for hydrazine in some cases. This deoxyamination features the involvement of a complex C-O bond and N-N/O bond-cleavage process and allows for the construction of N-substituted cyclohexyl anilines from an array of phenols by finely controlling the reaction conditions in moderate to good yields.