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Metathetical Redox Reaction of (Diacetoxyiodo)arenes and Iodoarenes.

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.

SUBMITTER: Jobin-Des Lauriers A

PROVIDER: S-EPMC6332457 | biostudies-literature | 2015 Dec

REPOSITORIES: biostudies-literature

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Metathetical Redox Reaction of (Diacetoxyiodo)arenes and Iodoarenes.

Jobin-Des Lauriers Antoine A Legault Claude Y CY

Molecules (Basel, Switzerland) 20151217 12

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. ...[more]

PMID: 26694343

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Project description:Iodosilarene derivatives (PhIO, PhI(OAc)2) constitute an important class of oxygen atom transfer reagents in organic synthesis and are often used together with iron-based catalysts. Since the factors controlling the ability of iron centers to catalyze alkane hydroxylation are not yet fully understood, the aim of this report is to develop bioinspired non-heme iron catalysts in combination with PhI(OAc)2, which are suitable for performing C-H activation. Overall, this study provides insight into the iron-based ([FeII(PBI)3(CF3SO3)2] (1), where PBI = 2-(2-pyridyl)benzimidazole) catalytic and stoichiometric hydroxylation of triphenylmethane using PhI(OAc)2, highlighting the importance of reaction conditions including the effect of the co-ligands (para-substituted pyridines) and oxidants (para-substituted iodosylbenzene diacetates) on product yields and reaction kinetics. A number of mechanistic studies have been carried out on the mechanism of triphenylmethane hydroxylation, including C-H activation, supporting the reactive intermediate, and investigating the effects of equatorial co-ligands and coordinated oxidants. Strong evidence for the electrophilic nature of the reaction was observed based on competitive experiments, which included a Hammett correlation between the relative reaction rate (logkrel) and the σp (4R-Py and 4R'-PhI(OAc)2) parameters in both stoichiometric (ρ = +0.87 and +0.92) and catalytic (ρ = +0.97 and +0.77) reactions. The presence of [(PBI)2(4R-Py)FeIIIOIPh-4R']3+ intermediates, as well as the effect of co-ligands and coordinated oxidants, was supported by their spectral (UV-visible) and redox properties. It has been proven that the electrophilic nature of iron(III)-iodozilarene complexes is crucial in the oxidation reaction of triphenylmethane. The hydroxylation rates showed a linear correlation with the FeIII/FeII redox potentials (in the range of -350 mV and -524 mV), which suggests that the Lewis acidity and redox properties of the metal centers greatly influence the reactivity of the reactive intermediates.

Dataset Information

Metathetical Redox Reaction of (Diacetoxyiodo)arenes and Iodoarenes.

Publications

Metathetical Redox Reaction of (Diacetoxyiodo)arenes and Iodoarenes.

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