Recent Progress in Cyclic Aryliodonium Chemistry: Syntheses and Applications

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(4), P. 1364 - 1416

Published: Jan. 17, 2023

Hypervalent aryliodoumiums are intensively investigated as arylating agents. They excellent surrogates to aryl halides, and moreover they exhibit better reactivity, which allows the corresponding arylation reactions be performed under mild conditions. In past decades, acyclic aryliodoniums widely explored However, unmet need for is improvement of their notoriously low reaction economy because coproduced iodides during often wasted. Cyclic have intrinsic advantage in terms economy, started receive considerable attention due valuable synthetic applications initiate cascade reactions, can enable construction complex structures, including polycycles with potential pharmaceutical functional properties. Here, we summarizing recent advances made research field cyclic aryliodoniums, nascent design aryliodonium species applications. First, general preparation typical diphenyl iodoniums described, followed by heterocyclic monoaryl iodoniums. Then, initiated arylations coupled subsequent domino summarized construct polycycles. Meanwhile, building biaryls axial atropisomers discussed a systematic manner. Finally, very advance employed halogen-bonding organocatalysts described.

Language: Английский

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Halogen, Chalcogen, Pnictogen, and Tetrel Bonding in Non‐Covalent Organocatalysis: An Update

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(31)

Published: May 11, 2024

The use of noncovalent interactions based on electrophilic halogen, chalcogen, pnictogen, or tetrel centers in organocatalysis has gained noticeable attention. Herein, we provide an overview the most important developments last years with a clear focus experimental studies and catalysts which act via such non-transient interactions.

Language: Английский

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Zwitterionic Dual Halogen Bond-Catalyzed Electrophilic Bromination of Electron-Deficient Arenes under Mild Conditions

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 4270 - 4279

Published: Feb. 25, 2025

Language: Английский

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A Bidentate Iodine(III)‐Based Halogen‐Bond Donor as a Powerful Organocatalyst**

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 60(10), P. 5069 - 5073

Published: Nov. 20, 2020

Abstract In contrast to iodine(I)‐based halogen bond donors, iodine(III)‐derived ones have only been used as Lewis acidic organocatalysts in a handful of examples, and all cases they acted monodentate fashion. Herein, we report the first application bidentate bis(iodolium) salt organocatalyst Michael nitro‐Michael addition reaction well Diels–Alder that had not activated by noncovalent before. cases, performance this XB donor distinctly surpassed one arguably currently strongest organocatalyst. Bidentate coordination substrate was corroborated structural analysis DFT calculations transition states. Overall, catalytic activity system approaches strong acids like BF 3 .

Language: Английский

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Modulating Chalcogen Bonding and Halogen Bonding Sigma‐Hole Donor Atom Potency and Selectivity for Halide Anion Recognition

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(40), P. 21973 - 21978

Published: July 23, 2021

A series of acyclic anion receptors containing chalcogen bond (ChB) and halogen (XB) donors integrated into a neutral 3,5-bis-triazole pyridine scaffold are described, in which systematic variation the electronic-withdrawing nature aryl substituents reveal dramatic modulation sigma-hole donor atom potency for recognition. Incorporation strongly electron-withdrawing perfluorophenyl units appended to triazole heterocycle telluro- or iodo- atoms, directly linked tellurium dramatically enhances binding receptors, most notably ChB XB displaying over thirty-fold eight-fold increase chloride affinity, respectively, relative unfluorinated analogues. Linear free energy relationships based halide recognition behaviour is highly sensitive local electronic environments. This especially case those Te centre (3⋅ChB), where remarkable enhancement strength selectivity lighter halides observed as ability Te-bonded group increases, highlighting exciting opportunity fine-tune affinity ChB-based receptor systems.

Language: Английский

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Iodine(III)‐Based Halogen Bond Donors: Properties and Applications

The Chemical Record, Journal Year: 2021, Volume and Issue: 21(8), P. 1912 - 1927

Published: June 18, 2021

Abstract Halogen bonding, the non‐covalent interaction of Lewis bases with an electron‐deficient region halogen substituents, received increased attention recently. Consequently, design and evaluation numerous halogen‐containing species as bond donors have been subject to intense research. More recently, organoiodine compounds at iodine(III) state receiving growing in field. Due their electronic structural properties, they provide access unique binding modes. For this reason, our groups involved development such compounds, quantification bonding strength (through acidities), well activities catalysts several model reactions. This account will describe these contributions.

Language: Английский

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Catalysis by Bidentate Iodine(III)-Based Halogen Donors: Surpassing the Activity of Strong Lewis Acids

The Journal of Organic Chemistry, Journal Year: 2021, Volume and Issue: 86(7), P. 5317 - 5326

Published: March 25, 2021

The poorly understood mode of activation and catalysis bidentate iodine(III)-based halogen donors have been quantitatively explored in detail by means state-of-the-art computational methods. To this end, the uncatalyzed Diels-Alder cycloaddition reaction between cyclohexadiene methyl vinyl ketone is compared to analogous process mediated a iodine(III)-organocatalyst related, highly active iodine(I) species. It found that iodine(III)-catalyst accelerates lowering barrier up 10 kcal mol-1 parent reaction. Our quantitative analyses reveal origin significant reduction steric (Pauli) repulsion diene dienophile, which originates from both more asynchronous polarization π-system dienophile away incoming diene. Notably, activity can be further enhanced increasing electrophilic nature system. Thus, novel systems are designed whose actually surpasses strong Lewis acids such as BF3.

Language: Английский

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Metal Centers as Nucleophiles: Oxymoron of Halogen Bond‐Involving Crystal Engineering

Chemistry - A European Journal, Journal Year: 2021, Volume and Issue: 28(2)

Published: Oct. 9, 2021

Abstract This review highlights recent studies discovering unconventional halogen bonding (HaB) that involves positively charged metal centers. These centers provide their filled d ‐orbitals for HaB, and thus behave as nucleophilic components toward the noncovalent interaction. role of some electron‐rich transition can be considered an oxymoron in sense is, most cases, formally cationic; consequently, its electron donor function is unexpected. The importance Ha⋅⋅⋅ ‐[M] (Ha=halogen; M Group 9 (Rh, Ir), 10 (Ni, Pd, Pt), or 11 (Cu, Au)) interactions crystal engineering emphasized by showing remarkable examples (reported uncovered our processing Cambridge Structural Database), where this directional interaction guides formation solid supramolecular assemblies different dimensionalities.

Language: Английский

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Diaryliodoniums as Hybrid Hydrogen- and Halogen-Bond-Donating Organocatalysts for the Groebke–Blackburn–Bienaymé Reaction

The Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 87(7), P. 4569 - 4579

Published: Feb. 17, 2022

Dibenziodolium and diphenyliodonium triflates display high catalytic activity for the multicomponent reaction that leads to a series of imidazopyridines. Density functional theory (DFT) calculations indicate both salts can play role hybrid hydrogen- halogen-bond-donating organocatalysts, which electrophilically activate carbonyl imine groups during process. The ortho-H atoms in vicinal position I atom dual role: forming additional noncovalent bonds with ligated substrate increasing maximum electrostatic potential on σ-hole at iodine owing effects polarization. triflate exhibits higher activity, results obtained from 1H nuclear magnetic resonance (NMR) titrations, conjunction those DFT calculations, this could be explained terms energy required rotation phenyl ring cation ligation substrate.

Language: Английский

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Sulfonium and Selenonium Salts as Noncovalent Organocatalysts for the Multicomponent Groebke–Blackburn–Bienaymé Reaction

The Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 87(15), P. 10199 - 10207

Published: July 20, 2022

Sulfonium and selenonium salts, represented by S-aryl dibenzothiophenium Se-aryl dibenzoselenophenium triflates, were found to exhibit remarkable catalytic activity in the model Groebke–Blackburn–Bienaymé reaction. Kinetic analysis density functional theory (DFT) calculations indicated that their effect is induced ligation of reaction substrates σ-holes on S or Se atom cations. The experimental data although 10-fold excess chloride totally inhibits sulfonium salt remains catalytically active, which can be explained experimentally lower binding constant derivative comparison with analogue. Both types salts than dibenziodolium species.

Language: Английский

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