Bromine radical release from a nickel-complex facilitates the activation of alkyl boronic acids: a boron selective Suzuki-Miyaura cross coupling

In this study, without utilizing any exogenous activator or strong oxidants, we successfully employed inactivated and easily accessible alkyl boronic acids (BAs) as coupling partners in a photocatalyzed Suzuki-Miyaura reaction under batch and continuous-flow conditions. Detailed mechanistic studies suggest a unique BA activation pathway, via a plausible radical transfer event between a bromine radical (formed in situ via a photo-induced homolysis of the Ni-Br bond) and the empty p-orbital on the boron atom. Subsequently, the necessity to tune the BA oxidation potential by means of hydrogen-bonding interaction with solvents or Lewis acid-base type interactions is replaced by a novel halogen radical transfer (XRT) mechanism. The mechanistic hypothesis has been supported by both control experiments and DFT calculations. © 2024 Elsevier B.V., All rights reserved.