Atom‐Economical Applications of Diaryliodonium Salts

Abstract

Diaryliodonium salt, as a stable and easily prepared reagent, has become one of the most efficient arylation reagents in organic synthesis. In traditional methods, this reagent is generally applied as a single arylation source and the regenerated aryl iodide is a waste of resources. In the past five years, transition-metal-catalyzed utilization of both aryl groups in diaryliodonium salts has been well demonstrated. The purpose of the present review is to focus on various atom-economical applications of diaryliodonium salt methodologies that have been reported recently for the synthesis of functionalized molecules. The presentation is organized according to the structures of the diaryliodonium salts and the reaction components.

Diaryliodoniums Salts as Coupling Partners for Transition-Metal Catalyzed C- and N-Arylation of Heteroarenes

“…Atom-economical strategies using hypervalent iodanes through domino or tandem processes represent an extremely attractive approach to avoid the waste of aryl iodide side-product [35,36]. The development of cascade reactions allowing the multiple formation of bonds starting from simple substrates in a single transformation consisting of at least two steps is a fairly appealing issue.…”

“…During the last decade, noteworthy improvement in the synthesis and use of diaryliodonium salts has been reported [9][10][11][12][13][14][15][16][17][18][19][20][21]. Owing to their electron-deficient nature at the iodine center and to the excellent leaving-group ability of the iodoarene, diaryliodonium salts are frequently employed as aromatic electrophiles in aryl transfer processes [22][23][24][25][26][27][28][29][30][31][32][33][34][35][36][37][38]. Seminal contributions from the Pike, Olofsson, Kita and Stuart groups highlighted the efficiency and the selectivity of this aforementioned reaction.…”

Hypervalent iodine compounds: reagents of the future

“…[37][38][39][40] Numerous recent reviews have been dedicated to synthetic applications of several specific classes of hypervalent iodine compounds. Aryliodonium salts have attracted significant interest as electrophilic arylating reagents [41][42][43][44][45][46][47] and precursors for Positron Emission Tomography (PET). 48,49 Iodonium ylides have also been recently utilized as PET precursors for nucleophilic radiofluorination.…”

Synthesis of Oxazoline and Oxazole Derivatives by Hypervalent-Iodine-Mediated Oxidative Cycloaddition Reactions

“…[31][32][33] The reactivity pattern of hypervalent iodine compounds is similar to that of transition-metal reagents. [34][35][36][37][38][39][40] Therefore, hypervalent iodine compounds have found wide application as efficient oxidative reagents and ligand transfer reagents in many reactions. [41][42][43][44][45][46][47][48][49] In fact, numerous oxidative reactions, benzyne-mediated reactions, and new bondforming reactions, such as carbon-carbon, carbon-heteroatom, or hetero-heteroatom bonds, have been accomplished using hypervalent iodine reagents under metal-free conditions.…”