Selective aerobic dehydrogenative aromatization to primary anilines catalyzed by palladium-based nanoparticles

Abstract In this study, we successfully developed aerobic dehydrogenative aromatization to primary anilines from various cyclohexanones and hydrazine (N2H4) in a one-pot manner by utilizing Al2O3-supported Au–palladium (Pd) alloy nanoparticle (Au–Pd/Al2O3) as the Pd-based catalyst. This reaction proceeded efficiently and selectively through dehydrogenation of stable azine intermediates followed by fast hydrogen transfer among intermediates for aromatization and N–N cleavage. Cyclohexylamines and cyclohexaneimines formed via N–N cleavage were also effectively dehydrogenated into primary anilines by Au–Pd/Al2O3 using O2 as the terminal oxidant.