Etherification of Fluoroarenes with Alkoxyboronic Acid Pinacol Esters via C–F Bond Cleavage

Potassium-base-mediated defluoroetherification of aryl and heteroaryl fluorides with alkoxyboronic acid pinacol esters under transition-metal-free conditions is reported. This protocol efficiently and safely provides a wide variety of aryl ethers in high yields without using metal catalysts, specific ligands, and harsh conditions to selectively forge C_sp2-O bonds via the C_sp2-F cleavage. This method can be applied to the late-stage etherification of structurally complex C_sp2-fluorides and bioactive alcohols, such as β-estradiol, calciferol, and tocopherol.