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

Tianfen Liu, Xuemei Zhang, Qingqing Wang, Zhong Lian

2025Angewandte Chemie International Edition12 citationsDOIOpen Access PDF

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.

Topics & Concepts

ArylCoupling reactionCoupling (piping)Combinatorial chemistryChemistryOrganic chemistryMaterials scienceCatalysisMetallurgyAlkylCatalytic C–H Functionalization MethodsCatalytic Cross-Coupling ReactionsRadical Photochemical Reactions