Transition Metal‐FreeO‐Arylation ofN‐Alkoxybenzamides Enabled by Aryl(trimethoxyphenyl)iodonium Salts

Abstract Herein, we develop a metal catalyst‐free protocol for O ‐arylation of benzamide hydroxamate esters. The chemoselective O ‐ versus N ‐arylation of the amides was tuned by varying the electronic and/or steric properties of the diaryliodonium salt and/or the substrate. The O ‐arylation reaction would preferentially occur for sterically and electronically diverse substrates. This study, which reveals the possibility of substituent‐ and reagent‐controlled chemoselectivity, with diaryliodonium salts might attract interest in the area of hypervalent iodine chemistry.