Dual Nickel(II)/Mechanoredox Catalysis: Mechanical-Force-Driven Aryl-Amination Reactions Using Ball Milling and Piezoelectric Materials.

Abstract

The combination of a nickel(II) catalyst and a mechanoredox catalyst under ball-milling conditions promotes mechanical-force-driven C-N cross-coupling reactions. In this nickel(II)/mechanoredox cocatalyst system, the modulation of the oxidation state of the nickel center, induced by piezoelectricity, is used to facilitate a highly efficient aryl-amination reaction, which is characterized by a broad substrate scope, an inexpensive combination of catalysts (NiBr2 and BaTiO3 ), short reaction times, and an almost negligible quantity of solvents. Moreover, this reaction can be readily up-scaled to the multi-gram scale, and all synthetic operations can be carried out under atmospheric conditions without the need for complicated reaction setups. Furthermore, this force-induced system is suitable for excitation-energy-accepting molecules and poorly soluble polyaromatic substrates that are incompatible with solution-based nickel(II)/photoredox cocatalysts.