Liquid-Assisted Grinding Enables Efficient Ni-Catalyzed, Mn-Mediated Denitrogenative Cross-Electrophile Coupling of Benzotriazinones with Benzyl Chlorides

An efficient and air-tolerant Ni-catalyzed denitrogenative cross-electrophile coupling of benzotriazinones with benzyl chlorides has been developed via liquid-assisted grinding by using Mn powders as reductant and DMF as assisting liquid in the presence of anhydrous calcium chloride. Scope and limitations of the protocol to access diarylmethanes have been demonstrated with more than 20 examples, showing acceptable tolerance to functional group and steric hindrance. Although electron-withdrawing substituents on benzotriazinone or benzyl counterparts decrease the yields significantly, a series of N-alkyl-2-benzylbenzamides, diarylmethanes bearing an ortho-carbamoyl aryl group, could be obtained in modest to good yields.