Solvent-modulated Binding Selectivity of Reaction Substrates to Onium-based Sigma-Hole Donors DOI Creative Commons
Alexandra A. Sysoeva, Alexander S. Novikov, Dmitrii S. Bolotin

et al.

Published: Dec. 20, 2022

Combination of experimental data and results DFT calculations indicates that the catalytic activity chalconium halonium salts served as sigma-hole donating organocatalysts cannot be clearly estimated via analysis electrostatic potential on catalysts’ sigma-holes values catalyst•••TS intermolecular interactions, such polarization effects, charge transfer, or covalency bonding. Moreover, real effect might not correlate well with Gibbs free energies activation reactions, because solvation effects other competitive binding processes play at least same even more important role in catalysis. It was showed present work, either can lead to increase equilibrium concentration reactive catalyst•••electrophile associates thus accelerating reaction brings favorable generation catalyst•••nucleophile species resulting suppression organocatalyst.

Language: Английский

Recent Progress in Cyclic Aryliodonium Chemistry: Syntheses and Applications DOI Creative Commons
Xiaopeng Peng, Abdur Rahim, Weijie Peng

et al.

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

Citations

71
Recent Progress in Synthetic Applications of Hypervalent Iodine(III) Reagents DOI Creative Commons
Akira Yoshimura, Viktor V. Zhdankin

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

Citations

28
Halogen, Chalcogen, Pnictogen, and Tetrel Bonding in Non‐Covalent Organocatalysis: An Update DOI Creative Commons
Dragana Jovanovic,

Meghana Poliyodath Mohanan,

Stefan M. Huber

et al.

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

Citations

27
Solvent-modulated binding selectivity of reaction substrates to onium-based σ-hole donors DOI
Alexandra A. Sysoeva, Alexander S. Novikov, Mikhail V. Il’in

et al.

Catalysis Science & Technology, Journal Year: 2023, Volume and Issue: 13(11), P. 3375 - 3385

Published: Jan. 1, 2023

Solvation effects might play the dominant role in catalysis providing an increase or suppression of activity organocatalysts.

Language: Английский

Citations

20
A Quantum‐chemical Analysis on the Lewis Acidity of Diarylhalonium Ions DOI Creative Commons
Raphaël Robidas, Dominik L. Reinhard, Stefan M. Huber

et al.

ChemPhysChem, Journal Year: 2022, Volume and Issue: 24(1)

Published: Aug. 31, 2022

Cyclic diaryliodonium compounds like iodolium derivatives have increasingly found use as noncovalent Lewis acids in the last years. They are more stable toward nucleophilic substitution than acyclic systems and markedly acidic. Herein, this higher acidity is analyzed explained via quantum-chemical calculations energy decomposition analyses. Its key origin change levels hybridization of iodine's orbitals, leading to both favorable electrostatic interaction better charge transfer. Both latter seem contribute similar fashion, while hydrogen bonding well steric repulsion with phenyl rings play at best a minor role. In comparison iodolium, bromolium chlorolium less acidic lighter halogen, which predominantly based on charge-transfer interactions.

Language: Английский

Citations

17
Unified strategy for the α-functionalization of esters, imides, and ketones via enolonium species DOI Creative Commons

Raja Kapanaiah,

Bat‐El Oded,

Raz Strugano

et al.

Cell Reports Physical Science, Journal Year: 2025, Volume and Issue: unknown, P. 102460 - 102460

Published: March 1, 2025

Language: Английский

Citations

0
Chiral Bromonium Salt (Hypervalent Bromine(III)) with N-Nitrosamine as a Halogen-Bonding Bifunctional Catalyst DOI Creative Commons
Yasushi Yoshida,

Tatsuya Ao,

Takashi Mino

et al.

Molecules, Journal Year: 2023, Volume and Issue: 28(1), P. 384 - 384

Published: Jan. 2, 2023

There has been a great focus on halogen-bonding as unique interaction between electron-deficient halogen atoms with Lewis basic moieties. Although the application of halogen-bonded in organic chemistry eagerly researched these decades, development chiral molecules functionalities and their utilization asymmetric catalysis are still the\ir infancy. We have previously developed halonium salts amide functionalities, which behaved excellent catalysts albeit only two reactions due to lack substrate activation abilities. In this manuscript, we an N-nitrosamine moiety applied them Mannich reaction isatin-derived ketimines malonic esters. The study focused our novel bromonium salt catalyst provided corresponding products high yields up 80% ee. DFT calculations structure suggested that induction abilities role part. To best knowledge, is first catalytic N-nitrosamines.

Language: Английский

Citations

9
An efficient and chemoselective method to generate arynes DOI Creative Commons

Bryan E. Metze,

Riley A. Roberts,

Aleksandra Nilova

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 14(47), P. 13885 - 13892

Published: Jan. 1, 2023

A chemoselective method to generate arynes by deprotonation of aryl(Mes)iodonium salts with potassium phosphate has been developed and was shown be one the most functional group compatible methods form these reactive intermediates.

Language: Английский

Citations

8
Nichtkovalente Organokatalyse mit Halogen‐, Chalkogen‐, Pniktogen‐ und Tetrelbrücken: neuere Entwicklungen DOI Creative Commons
Dragana Jovanovic,

Meghana Poliyodath Mohanan,

Stefan M. Huber

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(31)

Published: May 10, 2024

Abstract Die Anwendung nichtkovalenter Wechselwirkungen, welche auf elektrophilen Halogen‐, Chalkogen‐, Pniktogen‐ oder Tetrelzentren beruhen, hat in der Organokatalyse deutlich an Aufmerksamkeit gewonnen. Wir geben hier einen Überblick über die wichtigsten Entwicklungen letzten Jahre, mit einem Fokus experimentellen Studien und Katalysatoren, nicht‐transiente derartige Welchselwirkungen agieren.

Citations

2
Theoretical Quantification of the Lewis Acidity of N‐Heterocyclic Iodonium Salts DOI

Jiaqi Su,

Yubang Liu,

Yaru Jing

et al.

Asian Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 12(8)

Published: June 30, 2023

Abstract The quantitative Lewis acidity of N ‐heterocyclic iod(az)olium salts is helpful for their further application in organic chemistry. scales different ‐Heterocyclic iodonium (NHISs) acetonitrile are investigated using Density functional theory (DFT) studies. There a total 121 that have been designed by combining and salt structures this research. Theoretical calculations systematically established the 31 P NMR chemical shifts NHISs, relative scale was derived. trend analyzed explained natural population analysis (NPA) charges, molecular electrostatic potential, interaction between center substituents. This study expected to provide practical theoretical understanding design hypervalent iodine(III) reagents with versatile acidity.

Language: Английский

Citations

4