Synthesis of Phosphet-2-one Derivatives via Phosphinidene Transfer to Cyclopropenones

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(48), P. 25989 - 25994

Published: Nov. 27, 2023

We report the first synthesis and structural characterization of free, uncomplexed phosphet-2-ones. These unsaturated four-membered phosphacycles were prepared by phosphinidene transfer from dibenzo-7-phosphanorbornadiene compounds, RPA (A = C14H10, anthracene), to cyclopropenones in yields up 89%. Theoretical studies suggest that reaction proceeds through ketene-ylide ketene-phosphaalkene intermediates. Further transformations phosphet-2-ones led isolation more 1,2-dihydrophosphetes, including two furanone derivatives which are postulated be produced intramolecular phosphine-catalyzed [3 + 2] annulations.

Language: Английский

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Organophosphorus-Catalyzed Direct Dehydroxylative Thioetherification of Alcohols with Hypervalent Organosulfur Compounds

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(2), P. 1083 - 1090

Published: Jan. 4, 2024

A metal-free and thiol-free organophosphorus-catalyzed method for forming thioethers was disclosed, driven by PIII/PV═O redox cycling. In this work, one-step dehydroxylative thioetherification of alcohols fulfilled with various hypervalent organosulfur compounds. This established strategy features an excellent functional group tolerance broad substrate scope, especially inactivated alcohols. The scale-up reaction further transformation the product were also successful. Additionally, offers a protecting-group-free step-efficient approach synthesizing peroxisome proliferator-activated receptor agonists which exhibited promising potential treating osteoporosis in mammals.

Language: Английский

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P^III/P^V═O Redox Catalysis Mediated Thioesterification of Carboxylic Acids with Disulfides under Air Conditions

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 12, 2025

An efficient organophosphorus-catalyzed thiocarbonylation reaction of disulfides with carboxylic acids under air conditions was described. Various functional groups on and can be tolerated the present conditions, affording thioesters in good to excellent yields. This method exhibited chemoselectivity applied for late-stage functionalization drug molecules containing a acid group.

Language: Английский

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PPh₃‐Mediated Nucleophilic Sulfonation of Sulfonyl Chlorides with Arynes: Access to Manifold Aryl Sulfones

European Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 26(39)

Published: Aug. 19, 2023

Abstract Sulfonyl chlorides are a class of cheap and readily available basic chemicals, which have routinely served as electrophilic reagents in their chemical transformations. Herein, we disclose novel PPh 3 ‐mediated nucleophilic sulfonation method sulfonyl with arynes. Different from the classical P(III)‐mediated reductive deoxygenation reaction chlorides, valence state sulfur atom has not been changed. This protocol exhibits broad functional group tolerance provides direct approach to variety aryl alkyl sulfones.

Language: Английский

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P^III/P^V-Catalyzed Beckmann Reaction and Sequential [2,3]-Sigmatropic Rearrangement to Construct 2-Amidopyridines

Organic Letters, Journal Year: 2024, Volume and Issue: 26(17), P. 3536 - 3540

Published: April 24, 2024

An organophosphorus catalytic method for the synthesis of substituted 2-amidopyridines is reported. The employs a small-ring organophosphorus-based catalyst and hydrosilane reductant to drive conversion ketoximes pyridine-N-oxides into through sequential Beckmann rearrangement followed by [2,3]-sigmatropic rearrangement. readily available could be activated nitrilium ions in PIII/PV redox catalysis efficiently participate domino reaction pyridine-N-oxides, thus providing various moderate excellent yields. This presented strategy features functional group tolerance broad substrate scope.

Language: Английский

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5‐N,N‐Diarylaminothiazoles with Electron‐Accepting Groups: Synthesis, Photophysical Properties, and Their Application for the Detection of Hydrazine Hydrate

European Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 27(3)

Published: Nov. 8, 2023

Abstract 5‐N,N‐diarylaminothiazoles containing cyano and nitro groups were synthesized using the Pd‐catalyzed Buchwald‐Hartwig amination reaction with good yields. The group in resultant thiazole was reduced to a formyl group. This then subjected Knoevenagel condensation reaction, leading formation of thiazoles dicyanovinyl an amino group, which subsequently reacted triphosgene, yielding isocyanate These thiazoles, their electron‐accepting properties, demonstrated absorption emission spectra at longer wavelengths. Notably, displayed red emission. Tests for detection hydrazine, hazardous volatile organic compound, conducted thiazoles. results showed that effectively responded hydrazine hydrate, evidenced by changes spectra. change color also visibly detectable naked eye.

Language: Английский

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An Efficient Method for Thioesterification of Carboxylic Acid with Sulfenylchloride

Tetrahedron, Journal Year: 2024, Volume and Issue: unknown, P. 134422 - 134422

Published: Dec. 1, 2024

Language: Английский

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Pd(OAc)₂/Xantphos Catalyzed Reductive Coupling of Sulfonyl Chlorides: Synthesis of Thioethers by Sulphur Dioxide Extrusion

ChemistrySelect, Journal Year: 2023, Volume and Issue: 8(47)

Published: Dec. 15, 2023

Abstract Herein, we reported a successful cross coupling of aryl sulfonyl chlorides to forge thioether skeleton via Pd catalysis. This transformation proceeded in the presence Xantphos. Preliminary mechanism studies demonstrated dual roles Xantphos: (i) reductant that reduced radical thio radical; (ii) ligand promotes reactions.

Language: Английский

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