Recent Advances in Copper‐Catalyzed Etherification Reactions

The effective synthesis of ethers, which are prevalent structural motifs in innovative medicines, functional materials, agrochemicals, and natural products, is still of great interest. Copper catalysis has emerged as a potent and sustainable method for CO bond formation due to its abundance on Earth, redox flexibility, and compatibility with various substrates. Rapid advancements in ligand design, base and additive effects, cocatalysis, photoredox activation, and electrochemical routes have all contributed to the expansion of substrate scope and enhanced reaction efficiency in Cu‐catalyzed etherification over the past decade. These results collectively underscore the versatility of Cu in ether bond formation and its increasing significance in facilitating selective, efficient, and sustainable etherification methods, while also recognizing limitations and potential for future research. This review summarizes advances reported during the period 2016–2025 in Cu‐catalyzed etherification, covering C(sp ² )O and C(sp ³ )O bond formation, asymmetric etherification, photoredox‐assisted, electrochemical, and cooperative catalytic strategies, together with their mechanistic features, substrate scope, and synthetic applications.