Controlling Pd-Catalyzed N-Arylation and Dimroth Rearrangement in the Synthesis of <i>N</i>,1-Diaryl-1<i>H</i>-tetrazol-5-amines

The Pd-catalyzed N-arylation method for the synthesis of eighteen N,1-diaryl-1H-tetrazol-5-amine derivatives is reported. By running reactions at 35 °C, compounds were isolated as single isomers since undesired Dimroth rearrangement was completely suppressed. Furthermore, N,1-diaryl-1H-tetrazol-5-amines rationalized by conducting comprehensive experiments and NMR analysis well density functional theory (DFT) calculations thermodynamic stability compounds. It established that thermodynamically controlled, equilibrium reaction determined corresponding isomers. mechanism investigated additional DFT calculations, opening tetrazole ring shown to be rate-determining step. maneuvering subsequent rearrangement, two more acquired, which otherwise cannot synthesized employing C–N cross-coupling reaction.