Recent Progress in Synthetic Applications of Hypervalent Iodine(III) Reagents

Chemical Reviews, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 13, 2024

Hypervalent iodine(III) compounds have found wide application in modern organic chemistry as environmentally friendly reagents and catalysts. iodine are commonly used synthetically important halogenations, oxidations, aminations, heterocyclizations, various oxidative functionalizations of substrates. Iodonium salts arylating reagents, while iodonium ylides imides excellent carbene nitrene precursors. Various derivatives benziodoxoles, such azidobenziodoxoles, trifluoromethylbenziodoxoles, alkynylbenziodoxoles, alkenylbenziodoxoles group transfer the presence transition metal catalysts, under metal-free conditions, or using photocatalysts photoirradiation conditions. Development hypervalent catalytic systems discovery highly enantioselective reactions chiral represent a particularly recent achievement field chemistry. Chemical transformations promoted by many cases unique cannot be performed any other common, non-iodine-based reagent. This review covers literature published mainly last 7-8 years, between 2016 2024.

Language: Английский

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Activation of I₂ with Aryl Iodine(III) for the Iodination of Deactivated Arenes

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: March 18, 2025

A method for iodinating deactivated aryl rings is reported using a greatly reduced quantity of H2SO4 (<1 vol %) compared with traditional methods, which often requires it as bulk solvent. new iodine(III) system oxidizes I2 in organic solvents (CH2Cl2, CHCl3) trifluoroacetic anhydride water scavenger. Catalytic used the case highly rings. The oxidants 4-nitrophenyliodine bis(trifluoroacetate) (NPIFA), 3-iodosylbenzoic acid (3-IBA), and 2,4-dichloro-5-iodosylbenzoic (3-IBACl2) are applied based on separability reactivity target substrates, their forms recovered by simple acid/base extractions, demonstrating excellent reusability. Leveraging this, iodinated products isolated without need chromatography. suitable use under benchtop conditions exhibits high efficiency iodine oxidant, well positional selectivity substrates tested.

Language: Английский

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A decade of lessons in the activation of ArIL₂ species

Chemical Science, Journal Year: 2024, Volume and Issue: 15(11), P. 3784 - 3799

Published: Jan. 1, 2024

Developments in methods to increase the oxidative capacity of ArIL 2 reagents are discussed, with a focus on an understanding these species' behaviour from perspective iodine.

Language: Английский

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C–H, Si–H and C–F abstraction with an extremely electron poor I(iii) reagent

Dalton Transactions, Journal Year: 2023, Volume and Issue: 52(43), P. 15866 - 15870

Published: Jan. 1, 2023

The recently discovered I(III) reagent NO2-C6H4-I(OTf)2 is found to rapidly react with hydride sources, including HSiEt3 and relatively hydridic C-H precursors. These represent the first distinct reactions involving direct abstraction by under ambient conditions. Direct C-F also demonstrated, as well oxidation of cyclic alkenes aromatic rings, all representing new for demonstrating very high reactivity NO2-C6H4-I(OTf)2.

Language: Английский

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Electrophilic activation of molecular bromine mediated by I(iii)

Dalton Transactions, Journal Year: 2023, Volume and Issue: 52(44), P. 16472 - 16479

Published: Jan. 1, 2023

In pursuit of a genuine bromo-λ3-iodane, it has been found that the combination Br2 and electron deficient λ3-iodanes can result in delivery both bromine atoms from to range aryl substrates, some highly deactivated. These brominations occur rapidly common chlorinated solvents at room temperature be achieved with catalytic activation commercially available PhI(OAc)2 PhI(OTFA)2. para-NO2 substituted derivatives are employed direct bromination towards more deactivated substrates. The mechanism is discussed insights being made, however remains unclear.

Language: Английский

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