Mechanochemically Enabled Formal Reductive Cross‐Coupling Reaction Between Aryl Ethers and Aryl Fluorides

Abstract Reductive cross‐coupling reactions involving two electrophilic reagents have become increasingly important in modern synthetic chemistry. Previous studies have investigated electrophilic reagents featuring zero or one inactive bond; however, reactions involving electrophilic reagents with two inactive bonds remain unexplored. This study presents the first nickel‐catalyzed reductive cross‐coupling reaction under mechanical conditions, involving aryl ethers and aryl fluorides, both of which contain inactive bonds. The reaction successfully synthesized a series of multifunctional biphenyl compounds, specifically including several sparingly soluble substrates that are challenging to prepare in a solvent system. Mechanistic studies have demonstrated that nickel and magnesium play a crucial role in the activation of C─F bonds. This novel coupling reaction offers a beneficial approach for polymer degradation and the development of luminescent materials.