Synthesis of Aryl(2,4,6-trimethoxyphenyl)iodonium Trifluoroacetate Salts

Abstract

The direct synthesis of aryl(2,4,6-trimethoxyphenyl)iodonium trifluoroacetate salts from aryl iodides is described. Stoichiometric quantities of trifluoroacetic acid and trimethoxybenzene are used as the counteranion and auxiliary precursors, respectively, under oxidizing conditions. The reaction occurs at mild temperature, is broad in scope, and does not require a separate anion exchange step to install the trifluoroacetate group. The intermediacy of two distinct dicarboxy aryl-λ-iodanes is hypothesized in the mechanism.

Trimethoxyphenyl (TMP) as a Useful Auxiliary for in situ Formation and Reaction of Aryl(TMP)iodonium Salts: Synthesis of Diaryl Ethers

“…Diaryliodonium salts contain an aryliodonium leaving group that leads to mechanistic advantages over traditional halides: facile oxidative addition to first-row metals (i. e., copper) and increased scope in metal-free reactions (Scheme 1b). [7][8][9] We have an ongoing interest in the development of reactions to synthesize [10,11] and use [7b-d] aryl(TMP)iodonium salts, and herein we describe a methods to generate and use them in situ for phenol arylation. A potential solution is to form the diaryliodonium in situ and exploit the aforementioned advantages of the iodonium leaving group while using more readily abundant starting materials (Scheme 1c).…”

Visible‐Light‐Induced 3‐Component Synthesis of Sulfonylated Oxindoles by Fixation of Sulfur Dioxide

“…The reaction of phenyl(2,4,6‐trimethoxyphenyl)iodonium tosylate 4b afforded the sulfonylated oxindole 3a in 63 % yield with a selective transfer of the phenyl group over the electron‐rich 2,4,6‐trimethoxyphenyl moiety (TMP). Aryl(2,4,6‐trimethoxyphenyl)iodonium salts have been recently introduced as an attractive new class of chemoselective, iodonium salt‐derived aryl transfer reagents , , . In order to demonstrate the utility of such unsymmetrical salts in our 3‐component transformation, an additional reaction with the iodonium salt 4c was performed.…”

“…Aryl(2,4,6-trimethoxyphenyl)iodonium salts have been recently introduced as an attractive new class of chemoselective, iodonium salt-derived aryl transfer reagents. [39,41,42] In order to demonstrate the utility of such unsymmetrical salts in our 3-component transformation, an additional reaction with the iodonium salt 4c was performed. Also in this case a selective transfer of the desired aryl moiety was observed.…”

Hypervalent aryliodine compounds as precursors for radiofluorination

“…Recently, m CPBA in triflic acid has been found effective for the 1‐pot synthesis of a wide range of substituted aryl(2,4,6‐trimethoxyphenyl)iodonium triflates from iodoarenes . Trifluoroacetates have been prepared similarly by use of trifluoroacetic acid instead of triflic acid …”