Among the carbon-carbon (C-C) coupling reactions used for the synthesis of biaryls with a wide range of bioactivity, the most preferred method is the Suzuki-Miyaura (SM) reaction. The use of low-toxicity reagents and the fact that it is a type of reaction that occurs easily in moderate conditions increases the interest in this method. Palladium catalysts are preferred in the reaction. The N-Heterocyclic carbene (NHC)-Pd catalytic system, which is mostly preferred in the SM reaction, has the advantages of being able to easily change its electronic structure and not being sensitive to air and moisture when compared to other systems. In this sense, benzimidazole salts are useful precursors for the preparation of NHCs. The SM reaction in situ catalyzed by benzimidazolium halide-Pd(OAc)2 catalytic systems is the outstanding biaryl synthesis method today.