Air-Tolerant Nickel-Catalyzed Cyanation of (Hetero)aryl Halides Enabled by Polymethylhydrosiloxane, a Green Reductant

An air-tolerant nickel-catalyzed cyanation of aryl bromides is reported. The reaction uses a NiCl2/Xantphos catalyst in combination with substoichiometric quantities of zinc cyanide and polymethylhydrosiloxane. This silane is a green, homogeneous alternative to the traditional, insoluble solid reductant zinc and renders the reaction tolerant to air. The reaction can be performed under an air atmosphere, obviating the need for degassing, a glovebox, or Schlenk techniques. The reaction scope is broad, proceeding in good yields with a variety of (hetero)arenes.