Recognition in the Domain of Molecular Chirality: From Noncovalent Interactions to Separation of Enantiomers

Chemical Reviews, Journal Year: 2022, Volume and Issue: 122(16), P. 13235 - 13400

Published: Aug. 2, 2022

It is not a coincidence that both chirality and noncovalent interactions are ubiquitous in nature synthetic molecular systems. Noncovalent interactivity between chiral molecules underlies enantioselective recognition as fundamental phenomenon regulating life human activities. Thus, represent the narrative thread of fascinating story which goes across several disciplines medical, chemical, physical, biological, other natural sciences. This review has been conceived with awareness modern attitude toward its consequences needs to be founded on multidisciplinary approaches disclose basis essential phenomena domain With primary aim discussing this topic an integrated way, comprehensive pool rational systematic information provided, concerns fundamentals chirality, description interactions, their implications processes occurring different contexts. A specific focus devoted enantioselection chromatography electromigration techniques because unique feature "multistep" processes. second motivation for writing make clear statement about state art, tools we have at our disposal, what still missing fully understand mechanisms underlying recognition.

Language: Английский

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Cysteine-Activated Small-Molecule H₂Se Donors Inspired by Synthetic H₂S Donors

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(9), P. 3957 - 3967

Published: Feb. 22, 2022

The importance of selenium (Se) in biology and health has become increasingly clear. Hydrogen selenide (H2Se), the biologically available active form Se, is suggested to be an emerging nitric oxide (NO)-like signaling molecule. Nevertheless, research on H2Se chemical technique difficulties due lack well-characterized controllable donors under physiological conditions, as well a robust assay for direct quantification. Motivated by these needs, here, we demonstrate that selenocyclopropenones selenoamides are tunable donor motifs release upon reaction with cysteine (Cys) at pH 7.4 structural modifications enable rate Cys-mediated tuned. We monitored pathways confirmed generation qualitatively using different methods. further developed quantitative trapping quantitation aqueous solution, which should also operative investigating future motifs. In addition, arylselenoamide capability cellular environments. Importantly, mechanistic investigations density functional theory (DFT) calculations illustrate plausible Cys-activated from arylselenoamides detail, may help understand issues H2S pharmacologically important arylthioamides. anticipate well-defined chemistries will useful studying Se development new bioconjugate techniques.

Language: Английский

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Study and Applications of Tetrasubstituted Hypervalent Selenium–Halogen Species in Catalytic Electrophilic Halogenations

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(4), P. 2386 - 2395

Published: Feb. 1, 2023

Electrophilic halogenation reactions are highly useful in various areas. N-Haloamides commonly used as halogen sources because of high stability and commercial availability. In order to activate N-haloamides, Lewis basic chalcogens catalysts site-isolate the strongly coordinating amide moieties. However, corresponding trisubstituted chalcogenonium–halogen cationic intermediate is sensitive moisture nucleophiles, leading poor compatibility some reactions. Herein, we report an efficient catalytic protocol using phenyl selenium with ortho-substituted carboxylic acid catalyst. Mechanistic study suggests that a tetrasubstituted neutral hypervalent Se–halogen species responsible for reactivity. This active was found be moisture-stable, system applicable wide range electrophilic functionalization including haloamidation, intermolecular haloesterification, halocycloetherification, halolactonization, aromatic halogenation, halopolyene cyclization, selenylation

Language: Английский

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Solvent effect on the ⁷⁷Se NMR chemical shifts of diphenyl diselenides

New Journal of Chemistry, Journal Year: 2024, Volume and Issue: 48(7), P. 2971 - 2978

Published: Jan. 1, 2024

Herein, we evaluated the solvent effect on 77 Se NMR chemical shifts of diphenyl diselenides. To gain a deeper insight into shift behavior, DFT calculations have been performed.

Language: Английский

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Asymmetric Carbene Insertion into Se‐S Bonds by Synergistic Rh(II)/Guanidine Catalysis Involving Chalcogen‐Bond Assistance

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 2, 2024

The efficient construction of chalcogen-atom-based chiral compounds remains a challenge, despite the importance organoselenium and organosulfur in life materials science. Chalcogen atoms can form net attractive interactions called chalcogen bonds, but it is an undeveloped tool to assist asymmetric catalysis. Herein, we report enantioselective insertion platform install stereogenic center bearing selenyl thiocyano functional groups. Our method operates by synergistic catalysis guanidine achiral dirhodium complex three-component or four-component reaction, through Se-S bond into carbene species, competing successfully with spontaneous racemic process showing high regioselectivity. As elucidated spectroscopic experiments computational studies, unique mechanism involving as well hydrogen bonding was established account for enantiocontrol. stereoselectivity holds broad array selenylthiocyanatopropanoates, which showed excellent anti-inflammatory toward IL-1β low cytotoxicity.

Language: Английский

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Introduction of Methyl Group in Substituted Isoselenazolones: Catalytic and Mechanistic Study

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(7), P. 4273 - 4285

Published: March 17, 2023

Copper-catalyzed direct selenation of substituted 2-bromo-N-phenylbenzamide substrates with elemental selenium powder provided a series methoxy-substituted isoselenazolones via the C-Se and Se-N bond formations. Phenolic have been obtained by O-demethylation corresponding analogues using boron tribromide. Some structurally characterized X-ray single-crystal analysis. The glutathione peroxidase (GPx)-like antioxidant activity has evaluated both in thiophenol coupled-reductase assays. All showed good GPx-like activities assay. ferric-reducing power phenolic antioxidants also evaluated. best were found to be agents. single electron transfer, hydrogen atom proton-coupled transfer mechanisms for properties all catalysts supported density functional theory calculations. catalytic cycle was proposed one involving diselenide, selenenyl sulfide, selenol, selenenic acid as intermediates 77Se{1H} NMR spectroscopy.

Language: Английский

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Silver-catalyzed direct selanylation of indoles: synthesis and mechanistic insights

RSC Advances, Journal Year: 2023, Volume and Issue: 13(2), P. 914 - 925

Published: Jan. 1, 2023

Herein we describe the Ag(i)-catalyzed direct selanylation of indoles with diorganoyl diselenides. The reaction gave 3-selanylindoles high regioselectivity and also allowed access to 2-selanylindoles when C3 position indole ring was blocked

Language: Английский

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Aminic Organoselenium Compounds as Glutathione Peroxidase Mimics and Inhibitors of Ferroptosis

ChemBioChem, Journal Year: 2024, Volume and Issue: 25(4)

Published: Jan. 31, 2024

The synthesis of diarylamine-based organoselenium compounds via the nucleophilic substitution reactions has been described. Symmetrical monoselenides and diselenides were conveniently synthesized by reduction their corresponding selenocyanates using sodium borohydride. Selenocyanates obtained from 2-chloro acetamides displacement with potassium selenocyanate. Selenides treating in situ generated butyl selenolate as nucleophile. Further, newly evaluated for glutathione peroxidase (GPx)-like activity thiophenol assay. This study revealed that methoxy-substituted showed significant effect on GPx-like activity. catalytic parameters most efficient catalysts also determined. anti-ferroptotic all GPx-mimics a 4-OH-tamoxifen (TAM) inducible GPx4 knockout cell line liproxstatin standard.

Language: Английский

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Recent Advances in the Use of Diorganyl Diselenides as Versatile Catalysts

Molecules, Journal Year: 2023, Volume and Issue: 28(18), P. 6614 - 6614

Published: Sept. 14, 2023

The importance of organoselenium compounds has been increasing in synthetic chemistry. These reagents are well-known as electrophiles and nucleophiles many organic transformations, recent years, their functionality catalysts also largely explored. interest organoselenium-based is due to high efficacy, mild reaction conditions, strong functional compatibility, great selectivity. Allied catalysts, the use inorganic oxidants that act by regenerating catalytic species for pathway common. Here, we provide a comprehensive review last five years transformations promoted diorganyl diselenide selenium-based catalyst. This report divided into four sections: (1) cyclisation reactions, (2) addition reactions oxidative functionalisation, (3) oxidation reduction (4) involving phosphorus-containing starting materials.

Language: Английский

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New insights in the mechanism of the SARS-CoV-2 Mpro inhibition by benzisoselenazolones and diselenides

Scientific Reports, Journal Year: 2024, Volume and Issue: 14(1)

Published: Oct. 21, 2024

Although global vaccination campaigns alleviated the SARS-CoV-2 pandemic in terms of morbidity and mortality, ability virus to originate mutants may reduce efficacy vaccines, posing a serious risk renewed pandemic. There is therefore need develop small molecules capable targeting conserved viral targets, such as main protease (Mpro). Here, series benzisoselenazolones diselenides were tested for their inhibit Mpro; then most potent compounds measured antiviral activity vitro, mechanism action was investigated. Density functional theory calculations, molecular docking dynamics simulations also used elucidate protein/drug interaction. Finally, bio-organic model established study reaction between selenorganic biologically relevant thiols unveil possible metabolic pathways compounds. The overall results contribute identification novel Se-containing active against clarification some important aspects mechanisms inhibitors Mpro.

Language: Английский

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