Nickel-Catalyzed Sodium Hypophosphite-Participated Direct Hydrophosphonylation of Alkyne toward H-Phosphinates

The Journal of Organic Chemistry, Год журнала: 2023, Номер 88(6), С. 3539 - 3554

Опубликована: Фев. 24, 2023

The traditional methods for the synthesis of phosphinate esters use phosphorus trichloride (PCl3) as phosphorous source, resulting in procedures that are often highly polluting and energy intensive. search an alternative approach is both mild environmentally friendly a challenging, yet rewarding task modern chemistry. Herein, we inorganic phosphorous-containing species, NaH2PO2, to serve source participates directly nickel-catalyzed selective alkyne hydrophosphonylation reaction. transformation was achieved multicomponent fashion at room temperature, most importantly, H-phosphinate product generated advanced intermediate which can be readily converted into diverse derivatives, including those bearing new P–C, P–S, P–N, P–Se, P–O bonds, thus providing complimentary method classic ester techniques.

Язык: Английский

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Phosphoramidates as promising low-loading flame retardants for low density polyethylene

Polymer Degradation and Stability, Год журнала: 2025, Номер unknown, С. 111217 - 111217

Опубликована: Янв. 1, 2025

Язык: Английский

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Concept and Evolution of the Atherton-Todd Reaction

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 9660 - 9671

Опубликована: Май 22, 2025

Язык: Английский

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Atherton–Todd Reaction-Guided Enantioselective Synthesis of Axially Chiral Olefins via Bifunctional Phosphonium Salt-Regulating Ketone-Enol Tautomerism

ACS Catalysis, Год журнала: 2023, Номер 13(19), С. 13077 - 13088

Опубликована: Сен. 22, 2023

Atropisomerically enriched olefin scaffolds are of great importance in many fields chemistry. Although several synthetic routes to these axial molecules have been reported, alternative, powerful catalytic strategies still highly demanded this area. Here, we present an unprecedented organocatalytic method toward the atroposelective assembly axially chiral olefins with phosphorus unit via bifunctional phosphonium salt-catalyzed Atherton–Todd reaction ketones. This protocol provides a concise and efficient avenue allow access atropisomeric excellent stereoselectivities (up 99:1 e.r.). Moreover, experimental studies density functional theory (DFT) calculations revealed that coupling proceeded through dynamic kinetic resolution (DKR) process by phosphonium-controlled ketone-enol tautomerism also provided insights into origins formation axis. strategy offering convenient pragmatic route enantioenriched has never disclosed, providing platform for exploring potential applications olefin-containing molecules.

Язык: Английский

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Copper–cobalt double metal cyanides as green catalysts for phosphoramidate synthesis

Communications Chemistry, Год журнала: 2023, Номер 6(1)

Опубликована: Июль 5, 2023

Abstract Phosphoramidates are common and widespread backbones of a great variety fine chemicals, pharmaceuticals, additives natural products. Conventional approaches to their synthesis make use toxic chlorinated reagents intermediates, which sought be avoided at an industrial scale. Here we report the coupling phosphites amines promoted by Cu 3 [Co(CN) 6 ] 2 -based double metal cyanide heterogeneous catalyst using I as additive for phosphoramidates. This strategy successfully provides efficient, environmentally friendly alternative these valuable compounds in high yields it is, best our knowledge, first approach this protocol. While detailed study structure centers PXRD, FTIR, EXAFS XANES revealed changes coordination environment, maintained its activity least 5 consecutive iterations reaction. Preliminary mechanism studies suggest that reaction proceeds continuous change oxidation state metal, induced O /I − redox cycle.

Язык: Английский

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Recent Advances in the Use of Diorganyl Diselenides as Versatile Catalysts

Molecules, Год журнала: 2023, Номер 28(18), С. 6614 - 6614

Опубликована: Сен. 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.

Язык: Английский

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Electrochemical phosphorylation of arenols and anilines leading to organophosphates and phosphoramidates

Organic & Biomolecular Chemistry, Год журнала: 2021, Номер 19(24), С. 5342 - 5347

Опубликована: Янв. 1, 2021

A green, base- and oxidant-free phosphorylation for generating organophosphates phosphoramidates via electrochemical dehydrogenative cross-coupling of P(O)H compounds with arenols anilines was developed good functional group tolerance broad substrate scope.

Язык: Английский

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Enantiodivergent Kinetic Resolution of 1,1′‐Biaryl‐2,2′‐Diols and Amino Alcohols by Dipeptide‐Phosphonium Salt Catalysis Inspired by the Atherton–Todd Reaction

Angewandte Chemie, Год журнала: 2021, Номер 133(27), С. 15048 - 15057

Опубликована: Март 17, 2021

Abstract A highly enantiodivergent organocatalytic method is disclosed for the synthesis of atropisomeric biaryls via kinetic resolution inspired by a dipeptide‐phosphonium salt‐catalyzed Atherton–Todd (A‐T) reaction. This flexible approach led to both R ‐ and S ‐enantiomers fine‐tuning bifunctional phosphonium with excellent selectivity factors ( s ) up 1057 525, respectively. The potential newly synthesized O‐phosphorylated biaryl diols was illustrated axially chiral organophosphorus compounds. Mechanistic investigations suggest that halide catalyst differentiates between in‐situ‐generated P‐species in A‐T process, mainly involving phosphoryl chloride phosphoric anhydride, thus leading O‐phosphorylation reactions. Furthermore hydrogen bonding interactions catalysts phosphorus molecules were crucial asymmetric induction.

Язык: Английский

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S-(1,3-Dioxoisoindolin-2-yl)O,O-diethyl phosphorothioate (SDDP): A practical electrophilic reagent for the phosphorothiolation of electron-rich compounds

Chinese Chemical Letters, Год журнала: 2023, Номер 35(5), С. 109076 - 109076

Опубликована: Сен. 9, 2023

Язык: Английский

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Tf₂O-Mediated P(O)–N Bond Formation of Either P(O)–OH or P(O)–H Reagents with Multitype Amines

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(10), С. 6729 - 6739

Опубликована: Май 1, 2024

We have developed a Tf2O-mediated approach for the direct amination of either P(O)–OH or P(O)–H reagents with variety aliphatic aromatic amines. Without requirement precious metals and toxic reagents, this protocol provides an alternative route to various phosphinamides phosphoramides. The reaction proceeds under simple mild conditions can be effectively scaled up similar efficiency.

Язык: Английский

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