Nickel-Catalyzed Cross-Coupling of Phenols and Arylboronic Acids Through an In Situ Phenol Activation Mediated by PyBroP

A new method for the Suzuki–Miyaura cross‐coupling of phenols and arylboronic acids through in situ phenol activation mediated by PyBroP is presented. The reaction proceeds efficiently by using cost‐effective, markedly stable [NiCl2(dppp)] (dppp=1,3‐bis(diphenylphosphino)propane) as the catalyst in only 5 mol % loading, as well as in the absence of extra ligands. The method exhibits broad applicability and high efficiency towards a wide range of both phenols and boronic acids, including activated, nonactivated, deactivated, and heteroaromatic coupling partners. In addition, various functional groups, such as ether, amino, cyano, ester, and ketone groups, are compatible with this transformation. Notably, arylboronic acids containing an unprotected NH2 group and 2‐heterocyclic boronic acids, which are generally problematic for coupling under conventional conditions, are also viable substrates, although moderate yields were obtained for sterically hindered substrates. Consequently, the in situ cross‐coupling methodology coupled with the use of an inexpensive and stable nickel catalyst provides a rapid and efficient pathway for the assembly of biaryls and heterobiaryls with structural diversity from readily available phenol compounds. Phenol gets active…︁with nickel: A new method for the cross‐coupling of phenols and arylboronic acids through in situ phenol activation is presented. The reaction proceeds efficiently by using cost‐effective, markedly stable [NiCl2(dppp)] (dppp=1,3‐bis(diphenylphosphino)propane) as the catalyst in only 5 mol % loading, in the absence of extra ligands (see scheme). The method provides a rapid, straightforward pathway for the Suzuki–Miyaura cross‐coupling of phenol compounds.