Transition Metal‐Catalyzed Reactions with Iodine(III) Reagents

Abstract

AbstractTransition metal‐catalyzed functionalizations and heterocycle formations with hypervalent iodine reagents are discussed. The most important arylations of aromatic and heteroaromatic systems via cross‐coupling with diaryliodonium salts and CH bond activation are collected and described, focusing on the reaction mechanisms and the most important applications. Although the CC bond formations are the major parts of these transformations, the carbon–heteroatom bond‐forming reactions are also presented from two aspects. While the iodonium species provides the aryl group and reacts with nucleophilic heteroatom (oxygen or nitrogen), in the other approach, (diacetoxyiodo)benzene (DIB) serves as heteroatom donor to achieve acetoxylations of aromatic rings or the formation of three‐membered heterocycles (epoxides and aziridines) from unsaturated species. Due to the interaction of iodonium salts and special functional groups of the substrate, the initial CC or C–heteroatom bond formation could result in a reactive intermediate, which could induce a multiple bond‐formation relay to access special heterocyclic molecules.