Nickel-Catalyzed Aryl Group Interconversion: A Non-Equilibrium Strategy for Aryl Nitrile Synthesis.

Cross-electrophile coupling has become a powerful strategy for the construction of C-C bonds by linking two distinct electrophiles under metal catalysis. In contrast, aryl group interconversion reactions based on ligand exchange processes enable the direct swapping of aromatic groups between electrophilic partners, allowing the interconversion of different functional groups. Although these approaches can transform inexpensive substrates into high-value aromatic products, their inherent reversibility often requires excess reagents and relies on strong electronic bias between partners. Here, we describe a nickel-catalyzed aryl group interconversion between aromatic esters and 2-cyanopyridine. The process is driven by a decarbonylative ether formation step, which provides an irreversible pathway and establishes nonequilibrium conditions, eliminating the need for excess electrophiles. This method accommodates a wide range of aromatic esters and delivers pharmaceutically relevant nitriles with high efficiency. Mechanistic studies indicate that oxidative addition complexes derived from each electrophile undergo anionic CN/OPh ligand exchange, which serves as the key step that promotes the overall transformation.