Solvent-modulated Binding Selectivity of Reaction Substrates to Onium-based Sigma-Hole Donors DOI Creative Commons
Alexandra A. Sysoeva, Alexander S. Novikov, Mikhail V. Il’in

et al.

Published: Jan. 2, 2023

The combination of experimental data and results DFT calculations indicates that the catalytic activity chalconium halonium salts serving 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 energy activation reactions, because solvation effects other competitive binding processes play at least an equal even more important role in catalysis. It was shown present work can either lead to increase equilibrium concentration reactive catalyst•••electrophile associates, thus accelerating reaction, brings favorable generation catalyst•••nucleophile species resulting suppression organocatalyst.

Language: Английский

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
Activation of alkynes by chalcogen bonding: a Se⋯π interaction catalyzed intramolecular cyclization of 1,6-diynes DOI

Yuanling Pang,

Zhiguo Zhao, Yao Wang

et al.

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(82), P. 12278 - 12281

Published: Jan. 1, 2023

The activation of the triple bond alkynes was dominated by transition metals, while it is difficult for organocatalysts to play an effective role in this realm. Herein, we describe chalcogen bonding, and weak Se⋯π interaction capable catalyzing intramolecular cyclization 1,6-diynes, thus adding a new capability list supramolecular catalysis.

Language: Английский

Citations

6
Chalcogen Bond Catalysis with Telluronium Cations for Bromination Reaction: Importance of Electrostatic and Polarization Effects DOI
Yanjiang Wang, Chang Zhao, Wen‐Kai Chen

et al.

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 29(71)

Published: Sept. 25, 2023

Recently, chalcogen bond catalysts with telluronium cations have garnered considerable attention in organic reactions. In this work, catalysis on the bromination reaction of anisole N-bromosuccinimide (NBS) cationic has been explored density functional theory (DFT). The catalytic is divided into two stages: bromine transfer step and proton step. Based computational results, one can find rate-determining Moreover, present study elucidates that a stronger between NBS will give better performance. Additionally, work also clarified importance electrostatic polarization effects oxygen atom Te catalyst reaction. are significantly influenced by electron-withdrawing ability substitution groups catalysts. structure-property relationship strength bond, effect, effect performance established for design more efficient

Language: Английский

Citations

6
Affinity of Telluronium Chalcogen Bond Donors for Lewis Bases in Solution: A Critical Experimental‐Theoretical Joint Study DOI Creative Commons

Loïc Groslambert,

Yann Cornaton, Matej Ditte

et al.

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 30(7)

Published: Nov. 16, 2023

Telluronium salts [Ar

Citations

5
Double Chalcogen Bonding Recognition Arrays in Solution DOI Creative Commons
Deborah Romito,

Hanspeter Kählig,

Paolo Tecilla

et al.

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(60)

Published: July 26, 2024

N-substituted pyridino-based congeners of Ebselen, named here as Pyrselen, incorporating proximal Se and N atoms, undergo dimerization in solution the solid state through a dual donor-acceptor arrangement chalcogen bonding sites. Dimerization constants were measured within 5-50 M

Language: Английский

Citations

1
N-Coordinated tellurenium(ii) and telluronium(iv) cations: synthesis, structure and hydrolysis DOI Creative Commons
Martin Hejda, Lukáš Doležal, Jan Blahut

et al.

Dalton Transactions, Journal Year: 2023, Volume and Issue: 52(44), P. 16235 - 16248

Published: Jan. 1, 2023

A set of tellurenium and dichlorotelluronium cations supported by (N),C,N-chelating ligands was synthesized, their Lewis acidity ascertained the Gutmann–Beckett method hydrolysis described.

Language: Английский

Citations

2
Phenotellurazine redox catalysts: elements of design for radical cross-dehydrogenative coupling reactions DOI Creative Commons
Alina Paffen, Christopher Cremer, Frédéric W. Patureau

et al.

Beilstein Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 20, P. 1292 - 1297

Published: June 4, 2024

Redox active phenotellurazine catalysts have been recently utilized in two different cross-dehydrogenative coupling reactions. In this study, we revisit the design of redox catalysts. particular, investigate level cooperativity between Te- and N-centers, effect secondary versus tertiary heterocyclic non-heterocyclic structures, substitution patterns on catalytic activity.

Language: Английский

Citations

0
Solvent-modulated Binding Selectivity of Reaction Substrates to Onium-based Sigma-Hole Donors DOI Creative Commons
Alexandra A. Sysoeva, Alexander S. Novikov, Mikhail V. Il’in

et al.

Published: Jan. 2, 2023

The combination of experimental data and results DFT calculations indicates that the catalytic activity chalconium halonium salts serving 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 energy activation reactions, because solvation effects other competitive binding processes play at least an equal even more important role in catalysis. It was shown present work can either lead to increase equilibrium concentration reactive catalyst•••electrophile associates, thus accelerating reaction, brings favorable generation catalyst•••nucleophile species resulting suppression organocatalyst.

Language: Английский

Citations

0