Synthesis of Cyclic and Acyclic ortho‐Aryloxy Diaryliodonium Salts for Chemoselective Functionalizations

Two regioselective, high‐yielding one‐pot routes to oxygen‐bridged cyclic diaryliodonium salts and ortho‐aryloxy‐substituted acyclic diaryliodonium salts are presented. Starting from easily available ortho‐iodo diaryl ethers, complete selectivity in formation of either the cyclic or acyclic product could be achieved by varying the reaction conditions. The complimentary reactivities of these novel ortho‐oxygenated iodonium salts were demonstrated through a series of chemoselective arylations under metal‐catalyzed and metal‐free conditions, to deliver a range of novel, ortho‐functionalized diaryl ether derivatives.