Aryl halides are one of the most commonly used electrophilic reagents for metal-catalyzed coupling reactions. Due to their high synthesis cost and the production of stoichiometric halide fertilizers when participating in the reaction, the development of more sustainable and environmentally friendly alternatives to aryl halides has become one of the hot topics of research in recent years. Although cross-coupling of several phenol derivatives, which including aryl sulfonates, aryl esters and aryl carbamates, has been achieved in the past, the generation of sulfur-containing waste, coupled with high prices, has greatly reduced the application prospects of such substances. Aryl ethers are a basic and important class of raw materials and intermediates, as well as the simplest derivative of phenol. They are commercially available and inexpensive, and the absence of methoxy groups hardly causes any pollution to the environment. Therefore, it is of great significance to develop simple and efficient methods for catalytic conversion of aryl methyl ethers. Herein, we comprehensively summarize the research progress in the transformation reactions of aryl ethers via C—OMe bond cleavage in the past decade and classify them according to different reaction principles, including transition-metal catalyzed C—OMe bond transformation and transition-metal-free catalyzed/mediated C—OMe bond transformation (radical-mediated C—OMe bond transformation and Brønsted acid/base catalyzed C—OMe bond transformation). The reaction conditions, substrate tolerance, reaction mechanism, applications, and shortcomings are discussed in detail.

Key words: aryl ethers, aryl halide substitutes, C—OMe bond cleavage, transformation reactions