Synthesis Of Organophosphorus Compounds Research Articles

Development of novel syntheses of organophosphorus compounds: from a simple P-C bond formation to phosphacycles

Organophosphorus compounds play several essential roles in organic chemistry, such as valuable ligands in transition metal catalysis and functional materials. We have developed versatile organophosphine syntheses via Pd-catalyzed P-C cross-coupling reactions in the course of our study using silylphosphines. Up to three aryl groups can be selectively incorporated into the same phosphorus atom in a stepwise manner. In addition, we found the formation of phosphorus-ylide containing phosphacycles, λ5-phosphinines, during the extension of silylphosphine chemistry.

Alkali metal polyphosphides as intermediates in the synthesis of organophosphorus compounds from elemental phosphorus

Alkali metal polyphosphides as intermediates in the synthesis of organophosphorus compounds from elemental phosphorus

TiO2/Cu2O nanoparticle-catalyzed direct C(sp)–P bond formation via aerobic oxidative coupling in air and visible light

The synthesis of organophosphorus compounds is one of the important goals in organic chemistry. Among these compounds, alkynylphosphonates are significantly utilized as the main precursors for the synthesis of biologically active molecules in medicinal chemistry and have attracted extensive interest in the past few decades. Although few efforts have been made towards the direct and atom-economical synthesis of alkynylphosphonates, efforts towards the utilization of visible light as a green and renewable energy source have not been made to date. Here, we have promoted a strategy to construct a type of nano metal oxide composite photocatalyst (Cu2O decorated on TiO2) for the synthesis of alkynylphosphonates via direct C-P bond formation between terminal alkyne and H-phosphonate under visible light irradiation. In this p-n heterojunction photocatalyst, Cu2O acted as a visible-light absorber; moreover, the CB (conduction band) of TiO2 was favorable for accepting a photogenerated electron, and the generated electron hole (e-/h+) pair could initiate the reaction. The present study can provide a new way for the synthesis of this important class of phosphorus organic compounds.

Synthesis of diphenylphosphinic acid esters

<p>The development of new methods for the synthesis of organophosphorus compounds is still an important part of organic chemistry due to the high demand for these compounds in organic synthesis as well as in asymmetric catalysis. Most of the methods for the synthesis of these compounds include the reactivity of the phosphorus atom, which depending on the structure might exhibit both electrophilic and nucleophilic properties. Herein, I will present the results concerning synthesis of diphenylphosphinic acid esters.</p>

Synthesis of Organophosphorus Compounds through Copper-Catalyzed Annulation Involving C-O and C-P Bond Formations.

A novel copper(II) trifluoromethanesulfonate-catalyzed, high-efficiency, and atom-economical synthesis of valuable organophosphorus compounds via cascade annulation of propargylic alcohols with diphenylphosphine oxide is described. This protocol, which has a good functional-group compatibility and insensitivity to an ambient atmosphere, provides a simple and direct pathway to the products, organophosphorus compounds, in good yields under mild conditions. The method could be efficiently scaled up to gram scale, thus highlighting a potential application of this methodology.

Synthesis of organophosphorus compounds using ionic liquids

Abstract Organophosphorus chemistry was developed in the last decade by promoting the synthesis reactions using ionic liquids either as solvent or catalyst. Ionic liquids (ILs), the so-called “green solvents”, have gained interest in the synthesis of organophosphorus compounds as alternatives to flammable and toxic organic solvents and catalysts. ILs have beneficial properties because they provide high solubility for many organic and inorganic compounds or metal complexes, have no vapor pressure, and are reusable. Also, in some cases, they can enhance the reactivity of chemical reagents. In this review, we aimed at showing the synthesis of different organophosphorus compounds under green and mild conditions using ILs as reaction media or catalysts, according to a trend developed in the last years. A novel trend is to perform these syntheses under microwave irradiation conditions together with ILs as solvents and catalysts.

Photoredox Catalysis in Organophosphorus Chemistry

AbstractThe vernal blooming of green chemistry has contributed to the development of visible light catalysis. Active radical species are generated from catalytic amounts of photosensitizers, such as transition‐metal complexes and organic dyes, upon visible light irradiation. Stoichiometric amounts of oxidants, reductants, and radical initiators are avoided in most cases. Thus, reactions proceed under milder conditions with a broader functional group tolerance than found by other methods. Photoredox catalysis has been used to form C−C and C−X (X=O, N, and S) bonds but is comparably underdeveloped in organophosphorus chemistry. Herein, we summarize advances in photoredox catalysis that involve organophosphorus chemistry. The synthesis of organophosphorus compounds by photoredox catalysis, transition‐metal complex/photoredox dual catalytic systems, and photoredox catalysis with phosphorus organocatalysts are discussed. The shortcomings and possible future trends of this chemistry are also presented.

Recent Advances in the Synthesis of Organophosphorus Compounds via Cross Coupling between Readily Available Materials and P-H Compounds

Recent Advances in the Synthesis of Organophosphorus Compounds via Cross Coupling between Readily Available Materials and P-H Compounds

ChemInform Abstract: Carbon‐Hydrogen to Carbon‐Phosphorus Transformations

AbstractReview: literature published between 2008 and 2013; 97 refs.

Synthesis of organophosphorus compounds based on the reaction of elemental phosphorus with proton-donor reagents

Reaction of elemental (white) phosphorus with proton-donor reagents has been studied. The following organophosphorus compounds containing P-O and P-S bonds have been synthesized: metal hypophosphites and phosphites, and ammonium salts of O,O′-diesters of dithiophosphoric, S,S′-diphenyldithiophosphoric, S,S′-dialkyltetrathiophosphoric, O,O′-alkylidenedithiophosphoric acids, and octathiotetraphosphetane. The reaction products include highly efficient inhibitors of steel corrosion with carbonic acid and hydrogen sulfide as well as compounds showing fungicide, anticancer, and anti-inflammatory activity.

ChemInform Abstract: The 2‐Phosphaethynolate Anion: Convenient Synthesis and the Reactivity

AbstractReview: 25 refs.

ChemInform Abstract: Construction of Highly Substituted Pyrazole Derivatives with P—C Bond: Access to Racemic and Enantioselective Forms by Conjugate Addition of Diarylphosphane Oxides to α,β‐Unsaturated Pyrazolones.

Abstract The synthesis of organophosphorus compounds is of great importance to industrial, agricultural, and pharmaceutical chemistry. In this paper, we have reported the synthesis of highly substituted pyrazole derivatives through P–C bond formation under catalyst-free conditions. On the other hand, the first catalytic asymmetric version of this reaction has also been developed under catalysis by an isosteviol derived thiourea organocatalyst. The optically active phosphorus-containing compounds have been obtained in good chemical yields with moderate enantioselectivities.

Construction of highly substituted pyrazole derivatives with P–C bond: access to racemic and enantioselective forms by conjugate addition of diarylphosphane oxides to α,β-unsaturated pyrazolones

The synthesis of organophosphorus compounds is of great importance to industrial, agricultural, and pharmaceutical chemistry. In this paper, we have reported the synthesis of highly substituted pyrazole derivatives through P–C bond formation under catalyst-free conditions. On the other hand, the first catalytic asymmetric version of this reaction has also been developed under catalysis by an isosteviol derived thiourea organocatalyst. The optically active phosphorus-containing compounds have been obtained in good chemical yields with moderate enantioselectivities.

P-Arylation: Arynes to Aryl-Phosphonates, -Phosphinates, and -Phosphine Oxides

Synthesis of organo-phosphorus compounds and their application in organic synthesis and life sciences has been a topic of contemporary interest. Michaelis-Arbuzov reaction is the most extensively utilized method for their preparation, which works well only with aliphatic halides. Hence, relatively harsh reaction conditions using transition-metal-catalyzed P-arylation (Arbuzov/Hirao reaction) are used for the preparation of aryl-phosphorus compounds. Presented herein is a competent process for the synthesis of aryl-phosphonates, -phosphinates, and -phosphine oxides by making an efficient use of arynes for C-P bond construction.

Organophosphorus Synthesis Without Phosphorus Trichloride: The Case for the Hypophosphorous Pathway

The vast majority of organophosphorus compounds is currently synthesized from phosphorus trichloride (PCl3), even though the final consumer products do not contain reactive phosphorus–chlorine bonds. In order to bypass phosphorus trichloride, significant interest has been devoted to functionalizing elemental phosphorus (P4, the precursor to PCl3), red phosphorus (Pred), or phosphine (PH3). Yet, other industrial-scale precursors are hypophosphorous derivatives (H3PO2 and its alkali salts), but their use as phosphorus trichloride replacements has been completely overlooked. Here, the case is made for an alternative approach to the industrial synthesis of organophosphorus compounds based on hypophosphites.

ChemInform Abstract: The Application of Green Chemistry Methods in Organophosphorus Synthesis

AbstractReview: 179 refs.

Solvent-Free Conditions as an Eco-Friendly Strategy for Synthesis of Organophosphorus Compounds

A series of diverse NH- and CH-acids are used for a one-pot synthesis of stable phosphorus ylides and 1,4-diionic organophosphorus compounds by trapping of the zwitterionic intermediate from the reaction between triphenylphosphine and dialkyl acetylenedicarboxylates under solvent-free conditions. The structural geometry for one of the products was confirmed by single crystal X-ray diffraction analysis. Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.

The Synthesis of Organophosphorus Compounds from Phosphine and Alcohols in the Presence of Quinones and Redox Polymers on their Basis

<p>This article presents the synthesis of phosphoric acid esters from phosphoric hydrogen РН3 and aliphatic alcohols. The process is based on the oxidation of phosphine by quinones and redox polymers on the basis of mono- and disubstituted quinoid derivatives of monoethanolamine vinyl ether. Molecular iodine is used as a catalyst. Two-, three-, four- and multicomp onent systems are studied in order to determine optimal conditions of the oxidation of phosphine quinones and repoxpolymers on their basis. The rate and selectivity of reaction were monitored by the absorption of РН<sub>3</sub>. As alcohols used aliphatic alcohols: BuOH, PrOH, EtOH, MeOH. Organophosphorus compounds were analyzed by a chromatographic method. It was established that alcohol solutions of individual components of reactionary system (quinones, redox ionites or iodine) are characterized by a low activity in relation to phosphine. Organophosphorus compounds are formed in insignificant quantities. In the mixed alcohol<br /> solution of benzoquinone takes place PH<sub>3</sub> oxidation forming trialkylphosphates. Conversion of phosphine constitutes 80-100%. Increasing the concentration of reagents of catalytic system has a positive effect on the process as a whole. Similar patterns were obtained when redox monomers and polymers on the base of quinones in the presence of iodine were used as oxidants. Esters of phosphoric acid – dialkylphosphites and esters of phosphorous acid – trialkylphosphates were identified as organophosphorus compounds. By selecting a redox agent in a zone of the catalysis it is possible to direct process in the desirable direction. The most activity in the oxidation of phosphine by iodine-alcohol solutions of quinoid monomers and polymers, is exhibited by 2-[N-(2-vinyloxy) ethyl]amino-NQ and polymer on their basis. Results of our experiments and literature data on oxidation-reduction processes with participation of iodine and quinones in organic solutions allowed to propose the separate oxidation-reduction mechanism of formation of organophosphorus compounds. In investigated multicomponent systems, the synergetic effect is manifested which is reached at the expense of distribution of oxidation-reduction functions among iodine, quinones and its derivatives. In this report, for the first time, it is established reactionary ability of quinones and redox ionites on their basis in an oxidizing alkoxylation of phosphine to valuable esters of acids of phosphorus. Reaction can be used for purification of exhaust and technological gases from phosphine and its utilization.</p>

ChemInform Abstract: Synthesis of Organo-Phosphorus Compounds via the Coordination Spheres of Transition Metals: Some Non-Classical Examples

ChemInform Abstract: Synthesis of Organo-Phosphorus Compounds via the Coordination Spheres of Transition Metals: Some Non-Classical Examples

Synthesis of organophosphorus compounds containing different Y,C,Y-chelating ligands. Crystal structure of P ← N intramolecularly coordinated diselenoxophosphorane

The reactions of L 1–3Li salts containing different Y,C,Y-chelating ligands L 1 = 2,6-( t-BuOCH 2) 2C 6 H 3 - 1 , L 2 = 2,6-(MesOCH 2) 2C 6 H 3 - 1 and L 3 = 2,6-(Me 2NCH 2) 2C 6 H 3 - 1 with PCl 3 is reported. While the presence of ligands L 2,3 afforded the synthesis of dichlorophosphines L 2PCl 2 ( 2) and L 3PCl 2 ( 3), the use of ligand L 1 resulted to the isolation of O → P coordinated 1-chloro-7-( t-butoxymethyl)-3H-2,1-benzoxaphosphole ( 1) as the result of the cyclization type reaction of dichlorophosphines L 1PCl 2. The hydrolysis of compounds 1– 3 as well as the preparation of phosphanes L 2PH 2 ( 7), L 3PH 2 ( 8), L 2PH(SnMe 3) ( 9) and L 3PH(SnMe 3) ( 10) is also discussed. The presence of N → P coordination enabled the isolation of N → P coordinated diselenoxophosphorane L 3PSe 2 ( 11). Compounds 1– 11 were characterized by the help of multinuclear NMR spectroscopy, ESI mass spectrometry and the structure of compound 11 was established by X-ray diffraction analysis.