Adduct-catalyzed tandem electro-thermal synthesis of organophosphorus (III) compounds from white phosphorus

National Science Review, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 13, 2025

Electrooxidation strategies for synthesizing readily oxidizable products face notable challenges, especially when the oxidation potential of is lower than that reactants or high current densities are necessary. The electrooxidation synthesis trivalent organophosphorus compounds (OPCs (III)) from white phosphorus (P4) has demonstrated but hindered by selectivity issues due to over-oxidation. Herein, we report a tandem electro-thermal pathway addresses these challenges in producing OPCs (III) P4. process begins with an step generates stable transfer reagent, then thermochemically converted into various high-value (III). Utilizing hexafluoroisopropanol (HFIP) as nucleophile and optimizing tetrabutylammonium iodide (TBAI)-4-dimethylaminopyridine (DMAP)-adduct catalytic system, developed efficient electrophilic reagent via electrosynthesis. adduct facilitates P4 enhances nucleophilicity HFIP, thereby improving process. This approach supports density, scales up hundred-gram level without yield loss, remains compatible fluctuating green electricity.

Language: Английский

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Recent progress on the functionalization of white phosphorus in China

National Science Review, Journal Year: 2024, Volume and Issue: 11(6)

Published: May 2, 2024

Direct synthesis of organophosphorus compounds from white phosphorus represents a significant but challenging subject, especially in the context ongoing efforts to comprehensively improve phosphorus-derived chemical industry driven by sustainability and safety concerns. China is world's largest producer phosphorus, creating demand for green transformation this crucial feedstock. This review provides an overview advancements activation Chinese research teams, focusing on direct construction P‒C/N/O/S/M bonds phosphorus. Additionally, we offer some insights into prospective directions future. paper aims attract more researchers engage area, stimulating follow-up exploration fostering enduring advances.

Language: Английский

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Copper catalysed construction of C-P bond: C-H functionalization

Journal of Organometallic Chemistry, Journal Year: 2025, Volume and Issue: unknown, P. 123512 - 123512

Published: Jan. 1, 2025

Language: Английский

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Construction of Phosphorothiolated 2-Pyrrolidinones via Photoredox/Copper-Catalyzed Cascade Radical Cyclization/Phosphorothiolation

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(7), P. 4947 - 4957

Published: March 18, 2024

A photoredox/copper-catalyzed cascade radical cyclization/phosphorothiolation reaction of N-allylbromoacetamides and P(O)SH compounds has been established. broad range novel nonfluorine- or difluoro-substituted 2-pyrrolidinones bearing the C(sp3)-SP(O)(OR)2 moiety can be conveniently constructed in moderate to good yields under mild conditions. Importantly, most tested phosphorothiolated showed potent inhibitory effects toward both AChE BChE.

Language: Английский

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Advances and perspectives on photochemical/electrochemical synthesis of nitrogen, sulfur, and phosphorus heteroatom containing compounds from biomass-based feedstocks

Industrial Crops and Products, Journal Year: 2024, Volume and Issue: 222, P. 119738 - 119738

Published: Sept. 27, 2024

Language: Английский

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Direct conversion of various phosphate sources to a versatile P-X reagent [TBA][PO2X2] via redox-neutral halogenation

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: Feb. 26, 2025

Abstract Inorganic phosphates hold significant potential as ideal natural building blocks, forming a fundamental basis for organic and biochemical synthesis. However, their limited solubility, inherent chemical stability, low reactivity pose substantial challenges to converting into organophosphates under mild conditions. This study introduces an efficient method the direct conversion of P(V)-X reagents, [TBA][PO 2 X ] (X = Cl, F), via redox-neutral halogenation process. utilizes cyanuric chloride (or fluoride) reagent, in combination with 1-formylpyrrolidine tetrabutylammonium (TBAC), ambient The approach enables effective various P(V) sources, including orthophosphates, pyrophosphoric acid, Na 3 P O 9 5 . Furthermore, we demonstrate synthetic utility P(V)-Cl reagent phosphorylation diverse -, S N - C- nucleophiles. Key advantages this process include use inexpensive readily available chemicals, avoidance high-energy redox reactions, generation reactive yet stable reagent.

Language: Английский

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Intermolecular 1,2,4-Thiadiazole Synthesis Enabled by Enzymatic Halide Recycling with Vanadium-Dependent Haloperoxidases

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

Published: March 12, 2025

The enzymatic synthesis of heterocycles is an emerging biotechnology for the sustainable construction societally important molecules. Herein, we describe enzyme-mediated strategy oxidative dimerization thioamides enabled by halide recycling vanadium-dependent haloperoxidase enzymes. This approach allows intermolecular biocatalytic bond formation using a catalytic quantity salt and hydrogen peroxide as terminal oxidant. established method applied to diverse range generate corresponding 1,2,4-thiadiazoles in moderate high yields with excellent chemoselectivity. Mechanistic experiments suggest that reaction proceeds through two distinct sulfur halogenation events are critical heterocycle formation. Molecular docking provide insight into reactivity differences between biocatalysts used this study. Finally, developed preparative scale chemoenzymatic anticancer agent penicilliumthiamine B. These studies demonstrate promising platform

Language: Английский

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Straightforward Superbase-Mediated Reductive O-Phosphorylation of Aromatic and Heteroaromatic Ketones with Red Phosphorus in the Superbase Suspension KOH/DMSO(H2O)

Molecules, Journal Year: 2025, Volume and Issue: 30(6), P. 1367 - 1367

Published: March 18, 2025

It was shown for the first time that diaryl(hetaryl)ketones are capable of directly phosphorylating with red phosphorus in superbase suspension KOH/DMSO(H2O) at 85 °C 1.5 h to afford potassium bis(diaryl(hetaryl)methyl)phosphates were earlier inaccessible a yield up 45%. The ESR data demonstrate unlike previously published phosphorylation elemental phosphorus, this new reaction proceeds via single electron transfer from polyphospide anions diaryl(hetaryl)ketones. This is example C-O-P bond generation during strongly basic media, which usually provides C-P formation.

Language: Английский

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Bridging Homogeneous and Heterogeneous Catalysis: Ni@CPOL-dppp&PPh₃-Catalyzed Symmetric H-Phosphonate Diester Synthesis from Sodium Hypophosphite

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 7912 - 7918

Published: April 29, 2025

Language: Английский

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Beyond Triphenylphosphine: Advances on the Utilization of Triphenylphosphine Oxide

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(4), P. 2090 - 2103

Published: Jan. 25, 2024

Triphenylphosphine oxide is a well-known industrial waste byproduct, and thousands of tons it are generated every year. Due to its chemical stability limited applications, settlement this issue has drawn extensive attention from chemists. The reduction triphenylphosphine heretofore the most employed solution, well reviewed. In view our recent studies on selective efficient conversion Ph

Language: Английский

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