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

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
Chalcogen Bonding Catalysis: Tellurium, the Last Frontier? DOI Creative Commons
Patrick Pale, Victor Mamane

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 29(69)

Published: Sept. 25, 2023

Chalcogen bonding (ChB) is the non-covalent interaction occurring between chalcogen atoms as Lewis acid sites and or groups of able to behave bases through their lone pair π electrons. Analogously its sister halogen bonding, high directionality this was implemented for precise structural organizations in solid state solution. Regarding catalysis, ChB now accepted a new mode activation demonstrated by increased number examples last five years. In family catalysts, those based on tellurium rapidly appeared overcome lighter sulfur selenium counterparts. review, we highlight properties tellurium-based derivatives solution summarize start-of-the-art applications catalysis.

Language: Английский

Citations

32
A Hexavalent Tellurium-Based Chalcogen Bonding Catalysis Platform: High Catalytic Activity and Controlling of Selectivity DOI
Xinxin Li, Yi Liu, Wei Wang

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 13, 2025

Herein, we describe a hexavalent tellurium-based chalcogen bonding catalysis platform capable of addressing reactivity and selectivity issues. This research demonstrates that tellurium salts can serve as class highly active catalysts for the first time. The centers in these have only one exposed interaction site, thus providing favorable condition controlling reaction selectivity. advantages were demonstrated by their remarkable catalytic activity cyanidation difluorocyclopropenes through C-F bond activation, which otherwise low reactive under strong Lewis acids or inaccessible representative divalent/tetravalent donors. catalyst was further highlighted its capability to address previously unresolved problem associated with acid approach, upon using some less silyl enol ethers nucleophiles functionalization difluorocyclopropenes. generality this versatile application different systems. differentiate two similar free OH groups glycosyl acceptors achieve excellent regio- stereoselectivity synthesis disaccharides, tetravalent gave Mechanistic investigation suggests catalyst-glycosyl donor-acceptor ternary supramolecular complex is operative.

Language: Английский

Citations

1
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
Telluronium‐Catalyzed Halogenation Reactions: Chalcogen‐Bond Activation of N‐Halosuccinimides and Catalysis DOI Creative Commons

Loïc Groslambert,

Patrick Pale, Victor Mamane

et al.

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(43)

Published: May 24, 2024

The ability of triaryltelluronium salts to interact with N-halosuccinimides (NXS) through chalcogen bonding (ChB) in the solid state and solution is demonstrated herein. Cocrystals bearing two CF

Language: Английский

Citations

5
2‐Benzamide Tellurenyl Iodides: Synthesis and Their Catalytic Role in CO2 Mitigation DOI
Saket Jain, Monojit Batabyal, Raviraj Ananda Thorat

et al.

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 29(49)

Published: June 20, 2023

Benzamide-derived organochalcogens (chalcogen=S, Se, and Te) have shown promising interest in biological synthetic chemistry. Ebselen molecule derived from benzamide moiety is the most studied organoselenium. However, its heavier congener organotellurium under-explored. Here, an efficient copper-catalyzed atom economical method has been developed to synthesize 2-phenyl-benzamide tellurenyl iodides by inserting a tellurium into carbon-iodine bond of 2-iodobenzamides one pot with 78-95 % yields. Further, Lewis acidic nature Te center basic nitrogen synthesized 2-Iodo-N-(quinolin-8-yl)benzamide enabled them as pre-catalyst for activation epoxide CO2 at 1 atm preparation cyclic carbonates TOF TON values 1447 h-1 4343, respectively, under solvent-free conditions. In addition, 2-iodo-N-(quinolin-8-yl)benzamide also used activating anilines form variety 1,3-diaryl ureas up 95 yield. The mechanistic investigation mitigation done 125 NMR HRMS studies. It seems that reaction proceeds via formation catalytically active Te-N heterocycle, ebtellur intermediate which isolated structurally characterized.

Language: Английский

Citations

11
Cationic Hypervalent Chalcogen Bond Catalysis on the Povarov Reaction: Reactivity and Stereoselectivity DOI
Chang Zhao, Ying Li, Yanjiang Wang

et al.

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(24)

Published: Feb. 19, 2024

Abstract Chalcogen bond catalysis, particularly cationic hypervalent chalcogen is considered to be an effective strategy for organocatalysis. In this work, the catalysis Povarov reaction between N‐benzylideneaniline and ethyl vinyl ether was investigated by density functional theory (DFT). The catalytic involves cycloaddition process proton transfer process, rate‐determining step process. Cationic tellurium derivatives bearing CF 3 F groups exhibit superior activity. For step, Gibbs free energy barrier decreases as positive electrostatic potential of catalysts increases. More importantly, has a strong linear correlation with in catalyst‐substrate complex. Furthermore, reactions include endo pathway exo pathway. C−H⋅⋅⋅π interaction substituent aryl ring contributes endo‐selectivity reaction. This research deeper understanding providing insights designing high performance.

Language: Английский

Citations

4
A Fluorogenic Substrate for Quinoline Reduction: Pnictogen‐Bonding Catalysis in Aqueous Systems DOI Creative Commons
Giacomo Renno, Qingxia Zhang, Antonio Frontera

et al.

Helvetica Chimica Acta, Journal Year: 2024, Volume and Issue: 107(5)

Published: March 6, 2024

Abstract It is often said that pnictogen‐bonding catalysis, and σ ‐hole catalysis in general, would not work aqueous systems because the solvent interfere as an overcompetitive pnictogen‐bond acceptor. In this study, we show transfer of from hydrophobic solvents to possible by replacing only with hydrophilic substrates, without changing catalyst or reaction. This differs conventional covalent Lewis acid catalysts, which are instantaneously destroyed ligand exchange. With their water‐proof substituents place exchangeable ligands, supramolecular counterpart evinced catalyze hydrogenation quinolines neutral systems. To secure these results, introduce a water‐soluble fluorogenic substrate releases coumarin upon reduction instead activated quinolidiniums, stiborane catalysts deepened holes. They demonstrate can operate higher‐order architectures for under biologically relevant conditions, provide operational assay high‐throughput screening fluorescence imaging, situ conditions.

Language: Английский

Citations

4
Evidence for and evaluation of fluorine–tellurium chalcogen bonding DOI Creative Commons
R. Weiss, Emmanuel Aubert,

Loïc Groslambert

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 14(26), P. 7221 - 7229

Published: Jan. 1, 2023

In the field of noncovalent interactions, chalcogen bonding (ChB) involving tellurium atom is currently attracting much attention in supramolecular chemistry and catalysis. However, as a prerequisite for its application, ChB should be studied solution to assess formation and, if possible, evaluate strength. this context, new derivatives bearing CH

Language: Английский

Citations

10
Bidentate Ligand Driven Intramolecularly Te…O Bonded Organotellurium Cations from Synthesis, Stability to Catalysis DOI Open Access
Saket Jain, Saurabh Sandip Satpute, Raushan Kumar Jha

et al.

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 30(4)

Published: Nov. 15, 2023

Abstract A new series of unsymmetrical phenyl tellurides derived from 2‐ N ‐(quinolin‐8‐yl) benzamide ligand has been synthesized in a practical manner by the copper‐catalyzed method using diaryl ditelluride and Mg as reductant at room temperature. In order to augment Lewis acidity these newly formed monotellurides, have transformed into corresponding ‐(quinolin‐8‐yl)benzamide tellurium cations. Subsequently, acidic cations were used chalcogen bonding catalysts, enabling synthesis various substituted 1,2‐dihydroquinolines activating ketones with anilines under mild conditions. Moreover, cation also catalyzed formation β ‐amino alcohols high regioselectivity effectively epoxides Mechanistic insight 1 H 19 F NMR study, electrostatic surface potential (ESP map), control reaction which reacted explosively epoxide, suggested that enhanced center seems responsible for efficient catalytic activities conditions excellent trifluoromethyl , nitro, pyridylsubstitution, difficult access.

Language: Английский

Citations

7