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

и другие.

Опубликована: Дек. 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.

Язык: Английский

Zwitterionic Dual Halogen Bond-Catalyzed Electrophilic Bromination of Electron-Deficient Arenes under Mild Conditions DOI
Muyin Zhang, Zhihai Ke

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 4270 - 4279

Опубликована: Фев. 25, 2025

Язык: Английский

Процитировано

2

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

и другие.

Catalysis Science & Technology, Год журнала: 2023, Номер 13(11), С. 3375 - 3385

Опубликована: Янв. 1, 2023

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

Язык: Английский

Процитировано

20

Asymmetric Ion-Pairing in Stereoselective Vinyl Polymerization DOI
Cole C. Sorensen,

Caleb T. Kozuszek,

Meredith A. Borden

и другие.

ACS Catalysis, Год журнала: 2023, Номер 13(5), С. 3272 - 3284

Опубликована: Фев. 20, 2023

Controlling polymer tacticity is a key consideration in macromolecular synthesis due to the impact of stereochemistry on material's thermomechanical and optical properties. Recently, inspired by work small molecule catalysis, asymmetric ion-pairing has emerged as valuable approach control polymers made through chain growth polymerization vinyl monomers. This Perspective outlines some challenges inherent stereocontrol well highlights recent catalyst development area that enabled both configuration conformation polymers. Several synthetic opportunities mechanistic questions have been identified will expand synthesis.

Язык: Английский

Процитировано

15

Chalcogen- and Halogen-Bond-Donating Cyanoborohydrides Provide Imine Hydrogenation DOI
Mikhail V. Il’in, Yana V. Safinskaya, Denis A. Polonnikov

и другие.

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(5), С. 2916 - 2925

Опубликована: Фев. 19, 2024

Sulfonium, selenonium, telluronium, and iodonium cyanoborohydrides have been synthesized, isolated, fully characterized by various methods, including single-crystal X-ray diffraction (XRD) analysis. The quantum theory of atoms in molecules' analysis based on the XRD data indicated that hydride···σ-hole short contacts observed crystal structures each compound a purely noncovalent nature. telluronium provide significantly higher rate model reaction imine hydrogenation compared with sodium tetrabutylammonium cyanoborohydrides. Based NMR high-resolution electrospray ionization mass spectrometry indicating progress is accompanied cation reduction, mechanism involving intermediate formation elusive onium hydrides has proposed as an alternative to conventional electrophilic activation moiety its ligation cation's σ-hole.

Язык: Английский

Процитировано

5

Halonium, chalconium, and pnictonium salts as noncovalent organocatalysts: a computational study on relative catalytic activity DOI
Alexander S. Novikov, Dmitrii S. Bolotin

Organic & Biomolecular Chemistry, Год журнала: 2022, Номер 20(38), С. 7632 - 7639

Опубликована: Янв. 1, 2022

This theoretical study sheds light on the relative catalytic activity of pnictonium, chalconium, and halonium salts in reactions involving elimination chloride electrophilic activation a carbonyl group. DFT calculations indicate that for cationic aromatic onium salts, values electrostatic potential heteroatom σ-holes gradually increase from pnictogen- to halogen-containing species. The higher halogen atoms result overall these species, but case pnictonium chalconium cations, weak interactions side groups provide an additional stabilization effect reaction transition states. Based upon quantum-chemical calculations, phosphonium(V) arsenonium(V) is expected be too low obtain effective noncovalent organocatalytic compounds, whereas stibonium(V), telluronium(IV) iodonium(III) exhibit application as organocatalysts.

Язык: Английский

Процитировано

22

Iodonium and Telluronium Triflates Serving as Noncovalent Organocatalysts Provide Catalytic Effect in the Schiff Condensation Due to Different Reasons DOI
Ivan O. Putnin, Alexandra A. Sysoeva, Mikhail V. Il’in

и другие.

ChemCatChem, Год журнала: 2024, Номер unknown

Опубликована: Июнь 15, 2024

Abstract Sulfonium, selenonium, telluronium triflates, as well chloronium, bromonium, and iodonium triflates have been examined in the model Schiff condensation chalcogen‐ halogen bond donating organocatalysts, respectively. The kinetic data indicated that catalytic effect of salt is provided via decrease enthalpy activation reaction, whereas – unexpectedly caused by value entropy activation. In addition, it was experimentally shown activity sulfonium selenonium salts significantly lower than chloronium bromonium salts, but latter pair species less stable under reaction conditions former pair.

Язык: Английский

Процитировано

4

(Pre)association as a crucial step for computational prediction and analysis of the catalytic activity of σ-hole donating organocatalysts DOI
Denis A. Polonnikov, Mikhail V. Il’in, Yana V. Safinskaya

и другие.

Organic Chemistry Frontiers, Год журнала: 2022, Номер 10(1), С. 169 - 180

Опубликована: Ноя. 22, 2022

A suitable model for computational study giving reliable estimation of the catalytic effect σ-hole donating organocatalysts is suggested.

Язык: Английский

Процитировано

18

Halonium and Chalconium Salt-Catalyzed Schiff Condensation: Kinetics and DFT Insights into Organocatalyst Activity Parameters DOI
Alexandra A. Sysoeva, Yana V. Safinskaya, Mikhail V. Il’in

и другие.

Organic & Biomolecular Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

Chalconium and halonium salts catalyze Schiff condensation. Kinetic data DFT calculations show that the catalytic activity correlates with maximum electrostatic potential on σ-holes, whereas other factors are less significant.

Язык: Английский

Процитировано

0

Mechanistic Insight into Anion‐Binding Catalytic Living Cationic Polymerization DOI
Maosheng Li, Hongyu Li, Xiaoyong Zhang

и другие.

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(26)

Опубликована: Апрель 26, 2023

Exploiting non-covalent interactions to catalyze challenging ionic polymerizations is an ambitious goal but in its infancy. We recently demonstrated anion-binding catalysis as effective methodology enable living cationic polymerization (LCP) of vinyl ethers environmentally benign manner. Here, we further elucidate the structure-reactivity relationships elaborately designed seleno-cyclodiphosph(V)azanes catalysts and roles by a combined theoretical DFT study experimental study. The investigation suggests that distinct cis-cyclodiphosph(V)azane framework with "selenium effect" electron-withdrawing 3,5-(CF3 )2 -Phenyl substitution pattern catalyst enables critical contribution accessing excellent stability, anion affinity solubility under conditions. Thus, could leverage precisely control reversible transient dormant-active species equilibrium, allowing it dynamically bind, recognize pre-organize propagating monomer, thereby facilitating efficient chain propagation minimizing irreversible transfer events mild more in-depth understanding mechanism for catalytic LCP reported herein should help guide future design extend this concept broader systems where serve crucial intermediates.

Язык: Английский

Процитировано

7

Computational Study on the Route of Cooperative Organocatalysis Utilizing Thiourea and Halogen Bond Donor Mixture DOI
Alexander S. Novikov, Mikhail V. Il’in

Russian Journal of General Chemistry, Год журнала: 2024, Номер 94(S1), С. S129 - S137

Опубликована: Янв. 1, 2024

Язык: Английский

Процитировано

2