A Simple Protocol for the C‐N Cross‐Coupling of Aryl Chlorides with Amines Applying Ni/NHC Catalysis

An efficient protocol for the C−N cross‐coupling of aryl chlorides with (hetero)aryl‐ and alkyl amines under nickel catalysis has been developed. The main advantage of the protocol is the use of a self‐activated Ni/NHC catalytic system generated in situ from readily available bench‐stable air‐tolerant precursors: NiCl₂Py₂, IPr ⋅ HCl, and sodium tert‐butoxide. A mass spectrometry mechanistic study of the reaction system revealed the dynamics of competitive processes of Ni/NHC active species formation and degradation involving NHC reductive elimination reactions and tert‐butoxide base. Optimization of the NiCl₂Py₂/IPr ⋅ HCl/tBuONa ratio and the reaction temperature allowed efficient catalysis to be achieved. The developed simple protocol represents an alternative for methods relying on the use of air‐sensitive and unstable Ni(cod)₂ or expensive well‐defined Ni/NHC precatalysts.