Au-Catalyzed Aerobic Dehydrogenative Aromatization to m-Phenylenediamine Derivatives via Product Selectivity Control

m-Disubstituted arenes are important in various fields but difficult to be directly synthesized by classical methods in the case of two electron-donating substituents due to the o,p-orientation. Dehydrogenative aromatization from nonaromatic cyclohexenone motifs and nucleophiles via 1,2- and 1,4-addition to produce m-disubstituted arenes is promising as the novel process overcoming the intrinsic problems derived from using aromatic compounds as the substrates; however, there are no reports on tandem oxidation involving dehydrogenative aromatization for one-step synthesis via simultaneous 1,2- and 1,4-addition or m-phenylenediamine derivative synthesis because of the quite difficult product selectivity control. Here, by utilizing the unique dehydrogenation catalysis of CeO2-supported Au nanoparticles, we have developed one-step synthesis of various m-phenylenediamine derivatives via selective aerobic dehydrogenative aromatization from cyclohexenone motifs and secondary amines. In addition, the product selectivity switch to enaminones or N,N-disubstituted anilines was also achieved by tuning the reaction conditions.