A Highly Practical and Reliable Nickel Catalyst for Suzuki–Miyaura Coupling of Aryl Halides

Abstract We disclose that [1,3‐bis(diphenylphosphino)methane]nickel(II) chloride [NiCl 2 (dppp)] is a highly active, universally applicable, cheap, and stable catalyst for Suzuki–Miyaura cross‐coupling reactions of aryl halides with a catalyst loading of lower than 1 mol%, and more notably, in the absence of extra supporting ligands. Under the optimized reaction conditions, a broad range of aryl bromides as well as the notoriously unreactive aryl chlorides, including activated, non‐activated, deactivated, and heteroaromatic and sterically hindered substrates can be coupled smoothly with various boronic acids (47 examples, 48–98% yields). In addition, the transformation is tolerant of various functional groups such as ether, ester, ketone, aldehyde, cyano, and unprotected amino and hydroxy groups. Finally, the potential utilization of the methodology was further demonstrated by the gram‐scale synthesis of several core structures of commercialized antihypertensive drugs and fungicides. Thus, the combination of high activity, broad applicability, cheapness, and high stability of NiCl 2 (dppp) presented in this work constitutes one of the few prominent catalysts which allow for practical and reliable construction of biaryls and heterobiaryls with structural diversity from readily available aryl halides and boronic acids.