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 B₂pin₂ 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)₂Cl] and aryl radicals. Control experiments indicate that light promotes the reaction of [Ni^I(IMes)₂Cl] with aryl chlorides generating additional aryl radicals and [Ni^II(IMes)₂Cl₂]. The aryl radicals react with an anionic sp²-sp³ diborane [B₂pin₂(OMe)]^- formed from B₂pin₂ and KOMe to yield the corresponding borylation product and the [Bpin(OMe)]^•- radical anion, which reduces [Ni^II(IMes)₂Cl₂] under irradiation to regenerate [Ni^I(IMes)₂Cl] and [Ni(IMes)₂] for the next catalytic cycle.