Synthesis of Organoselenium Compounds with Elemental Selenium

Advanced Synthesis & Catalysis, Journal Year: 2021, Volume and Issue: 363(24), P. 5386 - 5406

Published: Nov. 20, 2021

Abstract In the recent decade, growing efforts have been devoted to employing elemental selenium as a source in organic synthesis. contrast unstable, smelly, and toxic previous reagents, is readily available, cheap, bench‐stable, easy handle. This review will mainly focus on strategies for activation of synthesis organoselenium compounds including monoselenides, diselenides, selenium‐containing heterocycles so on. magnified image

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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Heavy Chalcogen Properties of Sulfur and Selenium Enhance Nucleic Acid-Based Therapeutics

Biomolecules, Journal Year: 2025, Volume and Issue: 15(2), P. 218 - 218

Published: Feb. 2, 2025

The Group 16 elements of the periodic table have a characteristic valence shell configuration instrumental to their chemical properties and reactivities. electrostatic potentials these so-called chalcogens been exploited in design materials that require efficient passage electrons including supermagnets, photocatalytic dyes, solar panels. Likewise, incorporation heavy chalcogen selenium into organic frameworks has shown increase reactivities double bonds heterocyclic rings, while its interactions with aromatic side chains hydrophobic core proteins via selenomethionine impart stabilizing effect. Typically present active site, hypervalence selenocysteine enables it further stabilize folded protein mediate electron transfer. Selenium’s native occurrence bacterial tRNA maintains base pair fidelity, most notably during oxidative stress, through electronic steric effects. Such modifications at positions 2 5 uridine render sites relevant RNA-based therapeutics. Innocuous substitution for oxygen former standard methods selenium-derivatized oligonucleotide synthesis detection led establishment novel class In this review, we summarize some progress area.

Language: Английский

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CuBr₂-Catalyzed Annulation of 2-Bromo-N-Arylbenzimidamide with Se/S₈ Powder for the Synthesis of Benzo[d]isoselenazole and Benzo[d]isothiazole

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(4), P. 1963 - 1976

Published: Jan. 31, 2023

A CuBr2-catalyzed annulation of 2-bromo-N-arylbenzimidamide with selenium/sulfur powder for the synthesis benzo[d]isoselenazole and benzo[d]isothiazole in generally good yields was investigated. This synthetic strategy features substrate scope functional group tolerance. Furthermore, corresponding products could be converted into N-aryl indoles via rhodiumIII-catalyzed ortho C-H activation N-phenyl ring, providing an efficient approach axial aromatic molecules.

Language: Английский

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Phosphine-Catalyzed Dearomative [3 + 2] Cycloaddition of Benzoxazoles with a Cyclopropenone

Organic Letters, Journal Year: 2022, Volume and Issue: 24(5), P. 1127 - 1131

Published: Jan. 27, 2022

The triphenylphosphine-catalyzed dearomative [3 + 2] cycloaddition of benzoxazoles with 1,2-diphenylcyclopropenone is herein described. reaction scope, mechanism, and possible future applications this rare organocatalyzed are discussed.

Language: Английский

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Na₂S·9H₂O Enabled Defluorodisulfuration and Hydrodefluorination of Perfluorobutyl Tetralones: Synthesis of Trifluoromethyl 1,2-Dithioles

Organic Letters, Journal Year: 2023, Volume and Issue: 25(23), P. 4388 - 4393

Published: June 2, 2023

An unprecedented defluorocyclization of perfluorobutyl tetralones with Na2S·9H2O was developed for the synthesis trifluoromethyl 1,2-dithioles, which provided chemists novel access to biologically and pharmaceutically relevant organofluorides. Successive C(sp3)–F bond functionalization at perfluoroalkyl chain is vital formation four C–H/C–S/S–S bonds a five-membered S-heterocycle assembly. Cheap, weakly toxic, odorless inorganic sulfide acts as both disulfurating precursor hydrodefluorinating reagent in this tandem multi-bond-interconverting reaction.

Language: Английский

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Recent progress in cycloaddition reactions of cyclopropenone

Arabian Journal of Chemistry, Journal Year: 2024, Volume and Issue: 17(8), P. 105845 - 105845

Published: May 23, 2024

Cyclopropenone has emerged as a highly versatile precursor in organic synthesis due to its diverse reactivity. The cyclopropenone derivatives could undergo various transformations such cycloaddition reactions, ring-opening and isomerization reactions the presence of different chemical reagents. Over years, significant progress been made manipulation cyclopropenones for construction carbocycles, heterocycles, other useful compounds. Despite several reviews that have concerned chemistry cyclopropenones, utility motifs carbocycles heterocycles rarely reported. Herein, we report recent advancements synthetic precursors towards compounds with biological significance.

Language: Английский

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Heterocycles from cyclopropenones

RSC Advances, Journal Year: 2022, Volume and Issue: 12(29), P. 18615 - 18645

Published: Jan. 1, 2022

Great attention has been paid to cyclopropenones as they are present in many natural sources.

Language: Английский

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Imidazolium‐dithiocarboxylate zwitterions catalysed ring‐opening additions of cyclopropenones

Advanced Synthesis & Catalysis, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 23, 2025

Abstract Imidazolium‐dithiocarboxylate zwitterions (NHC ⋅ CS 2 ), a novel organocatalyst that derived from N‐heterocyclic carbene (NHC), was used to activate cyclopropenones. Under the catalysis of 10 mol% NHC 2, range phenols, alcohols, primary and secondary amines react with cyclopropenones produce trisubstituted α , β ‐unsaturated esters amides in 46–95% yield. More than 68 products, including 7 natural product derivatives have been synthesized through this method. Mechanism study showed act as Lewis base C=C double bond trigger ring‐opening reaction. HRMS analysis indicated formation key adduct cyclopropenone. importantly, demonstrated completely different catalytic activity catalysts, latter one cannot catalyse these reactions.

Language: Английский

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Palladium-Catalyzed Regioselective [3 + 2] Annulation with N-Allenamides at the Proximal C═C Bond: Synthesis of γ-Amino-α′-methylenecyclopentenones

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: April 10, 2025

A palladium-catalyzed [3 + 2] cycloaddition of cyclopropenones with N-allenamides has been developed. This methodology facilitates the synthesis γ-amino-α'-methylenecyclopentenones in moderate to excellent yields good regioselectivity and compatibility various functional groups. The employment as versatile 2C synthons enables simultaneous incorporation both a nitrogen atom methylene group into cyclopentenones. Furthermore, this approach exhibits reverse when compared general allenes. Density theory calculations successfully elucidated origin observed regioselectivity.

Language: Английский

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