Visible-Light-Induced Ni-Catalyzed Radical Borylation of Chloroarenes

A highly selective and general photoinduced C-Cl borylation protocol that employs [Ni(IMes)(2)] (IMes = 1,3-dimesitylimidazoline-2-ylidene) for the radical borylation of chloroarenes is reported. This photoinduced system operates with visible light (400 nm) and achieves borylation of a wide range of chloroarenes with B(2)pin(2) at room temperature in excellent yields and with high selectivity, thereby demonstrating its broad utility and functional group tolerance. Mechanistic investigations suggest that the borylation reactions proceed via a radical process. EPR studies demonstrate that [Ni(IMes)(2)] undergoes very fast chlorine atom abstraction from aryl chlorides to give [Ni-I(IMes)(2)Cl] and aryl radicals. Control experiments indicate that light promotes the reaction of [Ni-I(IMes)(2)Cl] with aryl chlorides generating additional aryl radicals and [Ni-II(IMes)(2)Cl-2]. The aryl radicals react with an anionic sp(2)-sp(3) diborane [B(2)pin(2)(OMe)](-) formed from B(2)pin(2) and KOMe to yield the corresponding borylation product and the [Bpin(OMe)](center dot-) radical anion, which reduces [Ni-II(IMes)(2)Cl-2] under irradiation to regenerate [Ni-I(IMes)(2)Cl] and [Ni(IMes)(2)] for the next catalytic cycle.