Metathetical Redox Reaction of (Diacetoxyiodo)arenes and Iodoarenes.

Antoine Jobin-Des Lauriers,Claude Legault

doi:10.3390/molecules201219874

Abstract

The oxidation of iodoarenes is central to the field of hypervalent iodine chemistry. It was found that the metathetical redox reaction between (diacetoxyiodo)arenes and iodoarenes is possible in the presence of a catalytic amount of Lewis acid. This discovery opens a new strategy to access (diacetoxyiodo)arenes. A computational study is provided to rationalize the results observed.

Highlights

In the recent years, the development of hypervalent iodine-mediated synthetic transformations has been receiving growing attention [1,2,3,4,5]
Hypervalent iodine reagents are a great alternative to toxic heavy metals often used to effect similar transformations [6,7,8,9,10]
The first example of such a metathetical redox reaction was reported by Koser et al, using [hydroxy(tosyloxy)-iodo] benzene (HTIB) as the oxidant, enabling transfer to a variety of iodoarenes (Scheme 1b) [16]

Summary

Introduction

The development of hypervalent iodine-mediated synthetic transformations has been receiving growing attention [1,2,3,4,5] This is not surprising considering the importance of improving oxidative reactions and reducing their environmental impact. The first example of such a metathetical redox reaction was reported by Koser et al, using [hydroxy(tosyloxy)-iodo] benzene (HTIB) as the oxidant, enabling transfer to a variety of iodoarenes (Scheme 1b) [16]. Two applications of this initial method were subsequently reported, including one example using [bis(trifluoroacetoxy)iodo]benzene (BTI) [17,18]. ResultSscahnemd eD1i.sCcuonscseiopnt and examples of metathetical redox reactions of iodanes and iodoarenes

Results and Discussion

Metathetical Redox Reaction of HTIB and p-Methyliodobenzene

One-Pot Metathetical Redox Reaction of DIB and o-Iodobenzoic Acid

Computational Details