Rhenium-Catalyzed [4 + 1] Annulation of Azobenzenes and Aldehydes via Isolable Cyclic Rhenium(I) Complexes.

The first Re-catalyzed [4 + 1] annulation of azobenzenes with aldehydes was developed to furnish 2H-indazoles via isolable and characterized cyclic Re(I)-complexes. For the first time, the acetate-acceleration effect is showcased in Re-catalyzed C-H activation reactions. Remarkably, mechanistic studies revealed an irreversible aldehyde-insertion step, which is in sharp contrast to those of previous Rh- and Co-systems.