Abstract: | A new catalytic system based on palladium‐amido‐N‐heterocyclic carbenes for Suzuki–Miyaura coupling reactions of heteroaryl bromides is described. A variety of sterically bulky, amido‐N‐imidazolium salts were synthesized in high yields from the corresponding anilines. This catalytic system effectively promoted Suzuki–Miyaura couplings of heteroaryl bromides and chlorides with a range of boronic acids to give the corresponding aryl compounds in high yield. The yield was increased with increasing steric bulkiness of the substituted group. Especially, 1‐(2,6‐diisopropylphenyl)‐3‐N‐(2,4,6‐tri‐tert‐butylphenylacetamido)imidazolium bromide ( 4bc ) exhibited 850,000 TON in the coupling reaction of 2‐bromopyridine and phenylboronic acid. In addition, pharmaceutical compounds such as milrinone and irbesartan were synthesized via Suzuki–Miyaura coupling using sterically bulky, amido‐N‐imidazolium salt ( 4bc ) as a ligand. |