Au-Catalyzed Unusual 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 the classical methods in the case of two electron-donating substituents due to the o,p-orientation. Dehydrogenative aromatization from non-aromatic 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 (one-step) synthesis via simultaneous 1,2- and 1,4-addition or m-phenylenediamine derivative synthesis via dehydrogenative aromatization because of the quite difficult product selectivity control. Here, by utilizing unique dehydrogenation catalysis of CeO2-supported Au nanoparticles, we have developed tandem aerobic oxidation to various m-phenylenediamine derivatives via selective 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 reaction conditions.