Chapter 4: Synthetic Methods for Diaryl Ether Preparation Using Arylating Reagents

Diaryl ethers are one of the most essential intermediates for organic synthesis in the fields of medicine, agrochemistry, and polymer sciences. There are many naturally occurring biologically active compounds bearing a diaryl ether group including the antibiotic vancomycin, perrottetines, and chloropeptins (anti-HIV agents). This chapter presents efficient and practical synthetic methods for the synthesis of diaryl ethers including Ullmann-type reactions of aryl halides which are achieved using copper catalysts, Buchwald–Hartwig cross-couplings of aryl halides in the presence of palladium catalytic systems, and Chan–Lam cross-couplings of phenols with arylboronic acids catalyzed by copper, nucleophilic aromatic substitution, the benzyne mechanism, S_NAr additions to metal-arene complexes, oxidative coupling reactions, and Fischer chromium carbene mediated benzannulation. The main objective of this section is to review the procedures used to synthesize diaryl ethers with special emphasis on recently reported catalytic procedures.