Synthesis of Non‐Symmetric Azoarenes by Palladium‐Catalyzed Cross‐Coupling of Silicon‐Masked Diazenyl Anions and (Hetero)Aryl Halides

The photoswitchable motif of azobenzenes is of great importance across the life and materials sciences. This maintains a constant demand for their efficient synthesis, especially that of non‐symmetric derivatives. We disclose here a general strategy for their synthesis through an unprecedented C(sp(2))−N(sp(2)) cross‐coupling where functionalized aryl‐substituted diazenes masked with a silyl group are employed as diazenyl pronucleophiles. These equivalents of fragile diazenyl anions couple with a diverse set of (hetero)aryl bromides under palladium catalysis with no loss of dinitrogen. The competing denitrogenative biaryl formation is fully suppressed. The reaction requires only a minimal excess, that is 1.2 equivalents, of the diazenyl component. By this, a broad range of azoarenes decorated with two electron‐rich/deficient aryl groups can be accessed in a predictable way with superb functional‐group tolerance.