Computational Prediction and Experimental Confirmation of the Reaction between 1-Lithio-1,3-Butadiene and White Phosphorus Affording Phospholyl Lithium DOI
Yaqi Zhao, Zhengqi Chai, Zhiyi Song

et al.

Organometallics, Journal Year: 2024, Volume and Issue: 44(1), P. 300 - 306

Published: Dec. 24, 2024

The direct construction of C–P bonds from white phosphorus (P4) and nucleophilic reagents is great scientific importance application value. In this work, density functional theory calculations reveal the reaction mechanism P4 with mono-lithium reagent, namely, 1,2,3,4-tetraethyl-1-lithiobuta-1,3-diene. realized through sequential attacks C–Li bond toward P–P butadiene skeleton. calculation results were confirmed by model 1,2,3,4-tetraethyl-1-lithiobuta-1,3-diene providing corresponding phospholyl lithium selectively. This work combining computational prediction experimental confirmation opens a new avenue for discovery selective between phosphorus.

Language: Английский

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

Jingcheng Hu,

Haoyu He,

Minghao Xu

et al.

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

Citations

3
A Tandem Route toward Isoxazolidine Fused Phospholene Skeleton Involving Dearomative [3+2] Cycloaddition of P‐Heteroarenes and Nitrones DOI Open Access

Chenyong Xu,

Y. Wang, Meng Xiao

et al.

Chinese Journal of Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 19, 2025

Comprehensive Summary The demands for effective assembly of structurally complex molecular scaffolds from simple starting materials are continuously growing along with the development organic chemistry. We have developed a tandem approach that assembles β ‐chloroethylphosphane, alkynyl imines (or ketones), and nitrones into isoxazolidine fused phospholene through sequential process involving phospha‐Michael addition, intramolecular cyclization, dearomatizing [3+2] cycloaddition reactions. isoxazolidine‐fused has three heteroatoms, including junction phosphorus atom. After removing coordinated tungsten group, these compounds can serve as potential P‐stereogenic ligands may biological activities. Contrary to pyrroles furans, aromatic 2‐phosphapyrroles 2‐phosphafurans good 2π‐electron candidates in dearomative reactions due poor overlap 2p‐3p orbitals C=P moiety.

Language: Английский

Citations

0
Multigram-Scale Synthetic Routes to Solvent-Free Common Secondary Dialkylphosphines and Chlorodialkylphosphines DOI Creative Commons
Amanda A. Fogh,

Sara Belazregue,

Andrew E. Ashley

et al.

Organometallics, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 20, 2025

Language: Английский

Citations

0
Straightforward Superbase-Mediated Reductive O-Phosphorylation of Aromatic and Heteroaromatic Ketones with Red Phosphorus in the Superbase Suspension KOH/DMSO(H2O) DOI Creative Commons
Vladimir A. Kuimov, Svetlana F. Malysheva, Nataliya A. Belogorlova

et al.

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

Citations

0
Chlorine-free synthesis of axially chiral organophosphorus compounds from white phosphorus DOI
Xinlei Huangfu, Yunguo Liu, Zhiyi Song

et al.

Chem, Journal Year: 2025, Volume and Issue: unknown, P. 102496 - 102496

Published: March 1, 2025

Language: Английский

Citations

0
Cu‐Catalyzed Allylic C─H Arylation of 3‐Phospholene Oxides with Triarylboroxines DOI
Ang Li, Guo‐Jie Wu, Fu‐She Han

et al.

ChemistrySelect, Journal Year: 2025, Volume and Issue: 10(20)

Published: May 1, 2025

Abstract A copper‐catalyzed oxidative allylic C─H arylation of 3,4‐diaryl‐3‐phospholene 1‐oxide derivatives with triarylboroxines is presented. Under the optimized conditions, reaction displayed a broad compatibility for both phospholene and boroxine substrates, affording 2‐monoarylated 2,5‐diarylated phosphole compounds in high overall yield (up to 74%), monoarylated products as major moderate moderately yields 58%). The scalability method was demonstrated by performing at gram‐scale level. In addition, versatile diversification also exemplified. Consequently, provides new route diverse synthesis structurally novel potentially useful 2,3,4‐triaryl‐substituted and, moreover, enriches methodology functionalization.

Language: Английский

Citations

0
Water mediated synthesis of dialkylphosphine oxides from white phosphorus and N-(acyloxy)phthalimides DOI Creative Commons
Guo Tang, Xinyu Zhu,

Jiali He

et al.

Organic Chemistry Frontiers, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

The first water mediated synthesis of dialkylphosphine oxides and α-hydroxy phosphine from P 4 without a chlorination step oxidation process is presented.

Language: Английский

Citations

0
Enchanting Realm of Five-Membered Rare-Earth Metallacycles DOI
Wei Liu, Dajiang Huang, Junnian Wei

et al.

Accounts of Chemical Research, Journal Year: 2025, Volume and Issue: unknown

Published: May 5, 2025

ConspectusMetallacycles, derivatives of carbocyclic compounds wherein a metal atom replaces at least one carbon center, have been constant powerhouse in organic synthesis. While metallacycles main-group, transition, and actinide metals extensively studied, those incorporating rare-earth (RE) elements (Sc, Y, lanthanides) remained elusive primarily due to synthetic challenges. Nevertheless, the electropositive character these resulting polarization RE-C bonds, along with intrinsic synergistic effects within metallacycles, endow RE unique properties rich, yet largely untapped, reaction chemistry. In this Account, we present development applications five-membered metallacycles.Over past decade, successfully synthesized variety all-carbon using two key strategies: (i) transmetalation, which has employed prepare metallacyclopentadienes spiro-metallacyclopentadienes, which, featuring various ligand systems, provide distinct coordination environments around significantly influencing their reactivity, (ii) transmetalation reduction, enabling synthesis spiro-metallacyclopentenes 2-butene tetraanion (BTA)-bridged dinuclear metallacyclopentenes. The reduction process proceeds via either self-disproportionation or by divalent centers alkali metals. These represent first instances such RE-containing metallacyclic ring structures.Our investigations into uncovered reactivities new modes. high reactivity multiple reactive sites enable them not only activate small molecules efficiently but also exhibit activation modes for some molecules. For instance, reactions carbodiimides showcase diverse insertion/rearrangement chemistry, influenced factors as number equivalents carbodiimide solvent choice. metallacyclopentadiene-mediated [3 + 1] fragmentation white phosphorus demonstrates an mode markedly different from that observed main-group transition analogs. Moreover, discovery cross-carbanion coupling RE-metal-mediated ring-opening metathesis benzene introduces modes, demonstrating that, rational design, can similar even surpassing further led chemistry.Additionally, novel uncovered, stemming geometric electronic structures. Structural analysis theoretical calculations revealed nonplanar aromaticity BTA-bridged metallacyclopentenes, extending concept chemistry carbon-RE metallacycles. Furthermore, benefiting redox capabilities butadiene dianion BTA ligands, ligand-based metallacyclopentenes efficient multielectron transfer processes, highlighting potential chemistry.The studies encompassing construction, characterization, properties, applications, greatly enriched field f-block We hope Account will inspire exploration organometallic reagents metallacycle-mediated transformations, fueling continued progress

Language: Английский

Citations

0
Phosphirane-Enabled Synthesis of Aromatic 1H-1,2-Azaphospholes and Phosphinines DOI

Chenyong Xu,

Zhipeng Dai,

Shaopeng Kang

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 6, 2024

Aromatic heteroarenes are essential components of numerous valuable molecules. Herein we present a simple and effective route to access aromatic 1H-1,2-azaphospholes phosphinines. This method utilizes the ring tension phosphiranes convert β-chloroethylphosphane alkynyl imines into these compounds. The nucleophilic addition phosphiranide complex results in 3, which transform under mild conditions. skeletal editing 1,2-azaphospholes phosphinine derivatives was accomplished through cascade process involving [4 + 2] cycloaddition elimination nitrogen moiety.

Language: Английский

Citations

2
Selective Functionalization of White Phosphorus with Alkyl Bromides under Photocatalytic Conditions: A Chlorine-Free Protocol to Dialkyl and Trialkyl Phosphine Oxides DOI

Jialiang Peng,

An Wang, Yan Liu

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(43), P. 9316 - 9321

Published: Oct. 24, 2024

A novel and efficient method for the direct selective alkylation of white phosphorus (P4) with alkyl bromides has been developed, utilizing 4DPAIPN as photocatalyst Hantzsch ester reductant. This facilitates synthesis structurally diverse dialkyl phosphine oxides in good yields, offering a streamlined alternative to traditional stepwise approach chlorinating P4 Cl2 subsequently displacing chlorine atom. Noteworthy features this reaction include excellent product selectivity, remarkable functional group tolerance, broad substrate scope. Additionally, is effective trialkyl oxides.

Language: Английский

Citations

1