Advancements in the Synthesis of Diaryliodonium Salts: Updated Protocols

Linde, Erika; Mondal, Shobhan; Olofsson, Berit

doi:10.1002/adsc.202300354

Cited by 11 publications

(2 citation statements)

References 53 publications

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“…The color of the products indicates that the reactions proceeded without any signs of decomposition, consequently yielding the desired products in high yields. However, the common synthetic methods of diaryliodonium(III) triflates involving a strong oxidizing agent with a strong acid and an electron-rich arene often resulted in black/discolored products, indicating decomposition, poor yields, and lower productivity in arylation processes [ 45 ].…”

Section: Resultsmentioning

confidence: 99%

Auxiliary strategy for the general and practical synthesis of diaryliodonium(III) salts with diverse organocarboxylate counterions

Miyamoto,

Koseki,

Sumida

et al. 2024

Beilstein J. Org. Chem.

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Diaryliodonium(III) salts are versatile reagents that exhibit a range of reactions, both in the presence and absence of metal catalysts. In this study, we developed efficient synthetic methods for the preparation of aryl(TMP)iodonium(III) carboxylates, by reaction of (diacetoxyiodo)arenes or iodosoarenes with 1,3,5-trimethoxybenzene in the presence of a diverse range of organocarboxylic acids. These reactions were conducted under mild conditions using the trimethoxyphenyl (TMP) group as an auxiliary, without the need for additives, excess reagents, or counterion exchange in further steps. These protocols are compatible with a wide range of substituents on (hetero)aryl iodine(III) compounds, including electron-rich, electron-poor, sterically congested, and acid-labile groups, as well as a broad range of aliphatic and aromatic carboxylic acids for the synthesis of diverse aryl(TMP)iodonium(III) carboxylates in high yields. This method allows for the hybridization of complex bioactive and fluorescent-labeled carboxylic acids with diaryliodonium(III) salts.

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Section: Resultsmentioning

confidence: 99%

Auxiliary strategy for the general and practical synthesis of diaryliodonium(III) salts with diverse organocarboxylate counterions

Miyamoto,

Koseki,

Sumida

et al. 2024

Beilstein J. Org. Chem.

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“…Diaryliodonium salts are useful alternatives to aryl halides, due to their increased reactivity; recently developed easy-to-oper-ate, one-pot synthetic approaches [47] to these compounds have greatly improved their synthetic applicability. Diaryliodonium salts readily form EDA complexes with nucleophiles as they contain a halogen bond donating iodine center.…”

Section: Diaryliodonium Saltsmentioning

confidence: 99%

Transition Metal and Photocatalyst Free Arylation via Photoexcitable Electron Donor Acceptor Complexes:Mediation and Catalysis

Volkov,

Bugaenko,

Karchava

2024

ChemCatChem

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Visible‐light‐activated organic reactions unlock novel avenues for molecular transformations, impossible under standard “thermal” conditions. However, transition‐metal‐based or organic photoredox catalysts are used to ensure productive absorption of visible light, which might be not desirable to medicinal chemistry and industry due to toxicity, low sustainability, and high cost of most photocatalysts. A more environmentally and economically benign approach is based on the formation of transient electron donor‐acceptor (EDA) complexes between the two reagents or a reagent and an additive, that readily absorb visible light, acting as the internal photosensitizers. Within the EDA complex‐based arylation strategies, the chemical transformations are mediated by noncovalent interaction between two molecules, namely between electron‐poor aryl halides or their synthetic equivalents and electron‐rich nucleophilic reagents or additives. Moreover, besides of stochiometric EDA complexes between two molecules, EDA complex‐based organocatalysis can be achieved in certain cases through regeneration of the donor molecules in the course of the reaction. Photoexcitation of the EDA complexes induces a single electron transfer (SET) process to generate aryl radical species for the arylation step. This Review will focus on the state‐of‐the‐art EDA complex‐based arylation strategies utilizing aryl halides, aryldiazonium, diaryliodonium, arylsulfonium and arylphosphonium salts as reactants, published mainly in the last five years.

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Arylation of Secondary Phosphines with Diaryliodonium Salts under Metal‐Free and Non‐Photochemical Conditions

Jha,

Sarkar,

Szczepanski

et al. 2024

Adv Synth Catal

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A new, efficient, as well as metal‐ and irradiation‐free approach for the direct arylation of secondary phosphines has been developed. The reaction employs diaryliodonium salts as electrophilic aryl‐transfer reagents, effecting the P–Ar bond‐formation in a single step, under mild conditions, using t‐BuOK as a base and DMSO as a solvent, at room temperature. The protocol furnishes expedient access to diverse unsymmetrical triarylphosphines and, upon a one‐pot oxidation, the corresponding triarylphosphine oxides. Experimental and computational studies support the inner sphere aryl‐transfer mechanism through a reductive coupling at the hypervalent iodine center. The calculations also point to a key role played by potassium ions, providing extra stabilization to the P–C bond‐forming transition state by binding the reactants via cation‐π interactions.

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Advancements in the Synthesis of Diaryliodonium Salts: Updated Protocols

Cited by 11 publications

References 53 publications

Auxiliary strategy for the general and practical synthesis of diaryliodonium(III) salts with diverse organocarboxylate counterions

Auxiliary strategy for the general and practical synthesis of diaryliodonium(III) salts with diverse organocarboxylate counterions

Transition Metal and Photocatalyst Free Arylation via Photoexcitable Electron Donor Acceptor Complexes:Mediation and Catalysis

Arylation of Secondary Phosphines with Diaryliodonium Salts under Metal‐Free and Non‐Photochemical Conditions

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