The Suzuki–Miyaura cross‐coupling (SMC) reactions of several heteroaryl chlorides, benzyl chlorides, and aryl acid chlorides with (hetero)arylboron reagents have been investigated in the presence of [Pd(HL1)(PPh3)Cl2] (I) [HL1 = 3‐[(2,6‐diisopropylphenyl)‐1‐imidazolio]‐2‐quinoxalinide] as catalyst and K2CO3 as base in neat water. The synthesis of the heterocycle‐containing biaryls required the addition of 2 mol‐% of a phosphine ligand (PPh3 or X‐Phos). A combination of more than 115 substrates were screened and it was found that I is a versatile catalyst that can produce heterocycle‐containing biaryls, diarylmethanes, and benzophenones in moderate‐to‐excellent yields.
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