- Synthesis of vinylphosphine oxides: vinyl selenides as vinylating agents
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2-(Alkylselanyl)ethyl(diorgano)phosphine selenides readily accessible from secondary phosphine selenides and alkyl vinyl selenides react with aqueous solution of hydrogen peroxide to form vinylphosphine oxides in high yields.
- Chernysheva, Nataliya A.,Yas'ko, Svetlana V.,Gusarova, Nina K.,Trofimov, Boris A.
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- New approach in the synthesis of hybrid polymers grafted with polyhedral oligomeric silsesquioxane and their physical and viscoelastic properties
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Synthesis, chain characteristics, and time-dependent viscoelastic response of polyhedral oligomeric silsesquioxanes (POSS)-containing hybrid polymers were investigated. Unlike many other reported POSS hybrid copolymers works, the POSS-grafted copolymers u
- Lee, Andre,Xiao, Jun,Feher, Frank J.
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Read Online
- Synthesis and extractive properties of dialkylaminomethyl-substituted dialkylamides of diphenylphosphinoylacetic acid
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Dialkylamides of diphenylphosphinoylacetic acids, dialkylaminomethyl-substituted by the methylene group, were prepared by means of the Mannich reaction from diphenyl(dialkylcarbamoylmethyl)-phosphine oxides or by reaction of the latter compounds with tetr
- Yarkevich,Turanov,Kharitonov
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Read Online
- New method for the syntheses of 2-aminoethyldiphenylphosphine oxides under the phase transfer conditions using cesium carbonate
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A simple one-pot method for the synthesis of 2-aminoethyldiphenylphosphine oxides is developed based on readily available diphenyl(2-phenoxyethyl)phosphine oxide and amines of different types under phase transfer catalysis conditions using anhydrous cesium carbonate as a base in acetonitrile or DMSO.
- Artyushin, Oleg I.,Belus', Svetlana K.,Bondarenko, Natalia A.,Tcarkova, Kseniia V.
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- 2-Phenoxyethyldiphenylphosphine oxide as an equivalent of diphenylvinylphosphine oxide in nucleophilic additions
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A facile method for the synthesis of β-functionalized ethyldiphenylphosphine oxides is developed based on readily available 2-phenoxyethyldiphenylphosphine oxide used as an equivalent of diphenylvinylphosphine oxide in the reactions of addition of different PH- and NH-nucleophiles in DMSO in the presence of KOH. The transformations of labile phosphine oxides of a general formula Ph2P(O)CH2CH2OR, where R = Ph, H, or Ph2P(O)CH = CH2, in aq.KOH/DMSO and solid KOH/DMSO systems are explored in the absence of nucleophilic reagents.
- Bondarenko, Natalia A.,Tcarkova, Kseniia V.,Belus', Svetlana K.,Artyushin, Oleg I.
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p. 902 - 910
(2021/06/25)
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- Knoevenagel Condensation of Phosphinoylacetic Acids with Aldehydes: An Efficient One-Pot Strategy for the Synthesis of P-Functionalized Alkenyl Compounds
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A wide range of commercially available aldehydes have been applied to Knoevenagel condensation reaction to give E -alkenylphosphine oxides and vinylphosphine oxides. The readily available phosphinoylacetic acids derived from P(O)-H compounds were used as the starting materials in the reaction, providing a highly stereoselective and efficient method for constructing α,β-unsaturated phosphine oxides. Moreover, this simple and practical procedure provides an alternative and more environmentally friendly synthesis strategy for this type of P-functionalized alkenyl compounds.
- Dziuba, Kamil,Frynas, S?awomir,Szwaczko, Katarzyna
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p. 2142 - 2154
(2021/01/21)
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- Engineering Catalysts for Selective Ester Hydrogenation
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The development of efficient catalysts and processes for synthesizing functionalized (olefinic and/or chiral) primary alcohols and fluoral hemiacetals is currently needed. These are valuable building blocks for pharmaceuticals, agrochemicals, perfumes, and so forth. From an economic standpoint, bench-stable Takasago Int. Corp.'s Ru-PNP, more commonly known as Ru-MACHO, and Gusev's Ru-SNS complexes are arguably the most appealing molecular catalysts to access primary alcohols from esters and H2 (Waser, M. et al. Org. Proc. Res. Dev. 2018, 22, 862). This work introduces economically competitive Ru-SNP(O)z complexes (z = 0, 1), which combine key structural elements of both of these catalysts. In particular, the incorporation of SNP heteroatoms into the ligand skeleton was found to be crucial for the design of a more product-selective catalyst in the synthesis of fluoral hemiacetals under kinetically controlled conditions. Based on experimental observations and computational analysis, this paper further extends the current state-of-the-art understanding of the accelerative role of KO-t-C4H9 in ester hydrogenation. It attempts to explain why a maximum turnover is seen to occur starting at 25 mol % base, in contrast to only 10 mol % with ketones as substrates.
- Dub, Pavel A.,Batrice, Rami J.,Gordon, John C.,Scott, Brian L.,Minko, Yury,Schmidt, Jurgen G.,Williams, Robert F.
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p. 415 - 442
(2020/03/04)
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- SYNTHESIS OF FLUORO HEMIACETALS VIA TRANSITION METAL-CATALYZED FLUORO ESTER AND CARBOXAMIDE HYDROGENATION
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This application is directed to use of transition metal-ligand complexes to hydrogenate fluorinated esters and carboxamides into fluorinated hemiacetals. Methods for synthesis of certain ligands are also provided.
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Paragraph 0191-0193
(2020/11/24)
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- Zero-Valent Amino-Olefin Cobalt Complexes as Catalysts for Oxygen Atom Transfer Reactions from Nitrous Oxide
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The synthesis and characterization of several zero-valent cobalt complexes with a bis(olefin)-amino ligand is presented. Some of these complexes proved to be efficient catalysts for the selective oxidation of secondary and allylic phosphanes, as well as diphosphanes, even with a direct P?P bond. With 5 mol % catalyst loadings the oxidations proceed under mild conditions (25–70 °C, 7–22 h, 2 bar N2O) and afford good to excellent yields (65–98 %). In this process, the greenhouse gas N2O is catalytically converted into benign N2and added-value organophosphorus compounds, some of which are difficult to obtain otherwise.
- Gianetti, Thomas L.,Rodríguez-Lugo, Rafael E.,Harmer, Jeffrey R.,Trincado, Monica,Vogt, Matthias,Santiso-Quinones, Gustavo,Grützmacher, Hansj?rg
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supporting information
p. 15323 - 15328
(2016/12/06)
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- FUMAGILLOL DERIVATIVES
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Disclosed are compounds of Formula (1), stereoisomers thereof and pharmaceutically acceptable salts of the compounds and stereoisomers, wherein R1 and R2 are defined in the specification. This disclosure also relates to materials and
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Paragraph 0161-0162
(2016/07/05)
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- POLYDENTATE LIGANDS AND THEIR COMPLEXES FOR MOLECULAR CATALYSIS
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The present invention relates generally to novel achiral and chiral sulfur-, nitrogen- and phosphorus-containing ligands, designated as NNS-type, P(0)NS-type, PNS-type, SNNS-type, SNNP(0)-type, or SNNP-type polydentate ligands and transition metal complexes of these ligands. The catalysts derived from these ligands and transition metal complexes may be used in a wide range of catalytic reactions, including hydrogenation and transfer hydrogenation of unsaturated organic compounds, dehydrogenation of alcohols and boranes, various dehydrogenative couplings, and other catalytic transformations.
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Page/Page column 63
(2016/01/01)
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- The mechanism of efficient asymmetric transfer hydrogenation of acetophenone using an iron(II) complex containing an (S, S)-Ph 2PCH2CH=NCHPhCHPhN=CHCH2PPh2 ligand: Partial ligand reduction is the key
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On the basis of a kinetic study and other evidence, we propose a mechanism of activation and operation of a highly active system generated from the precatalyst trans-[Fe(CO)(Br)(Ph2PCH2CH=N-((S,S)-C(Ph)H- C(Ph)H)-N=CHCH2PPh2)][BPh4] (2) for the asymmetric transfer hydrogenation of acetophenone in basic isopropanol. An induction period for catalyst activation is observed before the catalytic production of 1-phenethanol. The activation step is proposed to involve a rapid reaction of 2 with excess base to give an ene-amido complex [Fe(CO)(Ph 2PCH2CH=N-((S,S)-C(Ph)H-C(Ph)H)-NCH=CHPPh 2)]+ (Fep) and a bis(enamido) complex Fe(CO)(Ph2PCH=CH-N-(S,S-CH(Ph)CH(Ph))-N-CH=CHPPh2) (5); 5 was partially characterized. The slow step in the catalyst activation is thought to be the reaction of Fep with isopropoxide to give the catalytically active amido-(ene-amido) complex Fea with a half-reduced, deprotonated PNNP ligand. This can be trapped by reaction with HCl in ether to give, after isolation with NaBPh4, [Fe(CO)(Cl)(Ph 2PCH2CH2N(H)-((S,S)-CH(Ph)CH(Ph))-N=CHCH 2PPh2)][BPh4] (7) which was characterized using multinuclear NMR and high-resolution mass spectrometry. When compound 7 is treated with base, it directly enters the catalytic cycle with no induction period. A precatalyst with the fully reduced P-NH-NH-P ligand was prepared and characterized by single crystal X-ray diffraction. It was found to be much less active than 2 or 7. Reaction profiles obtained by varying the initial concentrations of acetophenone, precatalyst, base, and acetone and by varying the temperature were fit to the kinetic model corresponding to the proposed mechanism by numerical simulation to obtain a unique set of rate constants and thermodynamic parameters.
- Mikhailine, Alexandre A.,Maishan, Mazharul I.,Lough, Alan J.,Morris, Robert H.
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supporting information; experimental part
p. 12266 - 12280
(2012/09/22)
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- Reaction of divinyl telluride with secondary phosphine chalcogenides
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Divinyl telluride reacted with 2 equiv of diphenylphosphine sulfide in the presence of AIBN as radical initiator (63-68°C) to give the corresponding anti-Markovnikov adduct in 68% yield with high regioselectivity. Treatment of the addition product with aqueous hydrogen peroxide at room temperature afforded 71% of vinyldiphenylphosphine oxide. Radical addition of diphenylphosphine selenide to divinyl telluride (AIBN, 63-68°C) led to the formation of 1,1,3,3-tetraphenyldiphosphoxane 1,3-diselenide in 82% yield. Pleiades Publishing, Ltd., 2011.
- Gusarova,Chernysheva,Yas'ko,Klyba,Trofimov
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experimental part
p. 2506 - 2509
(2012/04/10)
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- A practical and efficient green synthesis of β-aminophosphoryl compounds via the aza-Michael reaction in water
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Biphasic systems room temperature imidazolium ionic liquid (RTIL)/water or water as a solvent significantly accelerate the addition of amines to vinylphosphoryl compounds hence opening green and effective synthesis of β-aminophosphoryl compounds in excellent yields over short reaction times. The application of water, being the cheapest and most non-toxic solvent, without any catalyst or co-solvent, is more advantageous as it provides a simple isolation procedure for products having high purity (> 95% according to the NMR data) via simple freeze-drying and does not require extraction with organic solvents. The solubility of the starting phosphorus substrate in water does not play crucial role in the reaction as it was demonstrated using water insoluble diphenylvinylphosphine oxide. In contrast to typical procedures, using a reactant ratio (vinylphosphoryl compound: amine) of 2:1 readily resulted in double phosphorylation of primary amines, including polyamines, in water.
- Matveeva, Ekaterina V.,Petrovskii, Pavel V.,Klemenkova, Zinaida S.,Bondarenko, Natalya A.,Odinets, Irina L.
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body text
p. 964 - 970
(2011/11/05)
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- Regio- and stereospecific cleavage of stannyloxiranes with lithium diphenylphosphide
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Unsubstituted or C-substituted stannyloxiranes reacted stereospecifically with lithium diphenylphosphide to give either β-hydroxyphosphane oxides resulting from α-opening or β-phosphanyl ketones by β-opening. Furthermore, the reactivities of distannyloxir
- Gonzalez-Nogal, Ana M.,Cuadrado, Purification,Sarmentero, M. Angeles
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scheme or table
p. 850 - 859
(2009/07/17)
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- Reactions of phosphonioalkyl derivatives of phenylhydrazine and hydroxylamine
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Triphenyl- and tributyl[2-(2-phenylhydrazino)ethyl]phosphonium salts undergo dehydrogenation on heating to form the corresponding phenylhydrazones in high yields. The phenylhydrazone formed from the triphenylphosphonium salt can also be prepared from trip
- Ovakimyan,Barsegyan,Kikoyan,Indzhikyan
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p. 1069 - 1073
(2007/10/03)
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- Regio- and stereospecific cleavage of silyl- and disilylepoxides with lithium diphenylphosphide
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Unsubstituted or α- and β-C-substituted silylepoxides react stereospecifically with lithium diphenylphosphide, optionally followed by methylation, to give vinylphosphonium iodides or vinylphosphine oxides resulting from α-opening and silyl enol ethers, vi
- Cuadrado, Purificacion,Gonzalez-Nogal, Ana M.,Sarmentero, M. Angeles
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p. 4491 - 4497
(2007/10/03)
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- The first tridentate phosphine ligand combining planar, phosphorus and carbon chirality
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Two new diastereomerically pure tridentate phosphine ligands combining planar, phosphorus and carbon chirality have been conveniently synthesized via resolution of their phosphineoxide-diborane adducts and structurally characterized by X-ray analyses.
- Barbaro, Pierluigi,Bianchini, Claudio,Giambastiani, Giuliano,Togni, Antonio
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p. 2672 - 2673
(2007/10/03)
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- Reactivity of lithium diphenylphosphonium diylides towards phosphorus electrophiles: Synthesis of α,β-unsaturated phosphorus compounds
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The study of the reactivity of non-stabilized, semi-stabilized and stabilized lithium diphenylphosphonium diylides 1-4 towards Ph2PCl, allowed the synthesis of various α,β-unsaturated phosphines 13-14, via the intermediate formation of the corresponding functionalized monoylides 9-10 and their in situ reaction with carbonyl compounds. In many cases, the reaction is Z-stereoselective and the created double bond can be di- or also trisubstituted. The precise 1H-NMR study of the phosphines 13a-d and the X-ray analysis of 13a (Z isomer) allowed us to assign without ambiguity the stereochemistry of these compounds and to solve a 1H-NMR question. Contrary to reported results in the literature for 13a, we have shown that for the double bond of this phosphine, there is no exception to the general rule 3JHH(trans) > 3JHH(cis). The extension of this reactivity study to other phosphorus electrophiles such as Ph2P(O)Cl, Ph2P(S)Cl and (EtO)2P(O)Cl allowed, as preliminary results, the E-stereoselective synthesis of styrylphosphine oxide and sulfide and diethyl styrylphosphonate.
- Taillefer, Marc,Cristau, Henri Jean,Fruchier, Alain,Vicente, Virginie
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p. 307 - 315
(2007/10/03)
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- Iodosobenzene and iodoxybenzene as reagents for oxygen transfer in organophosphorus chemistry
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The application of iodosobenzene (1) and iodoxybenzene (2) for the oxidation reaction of phosphorous, phosphorothiono and phosphoroseleno compounds into the corresponding ≡P(O) analogs is demonstrated. Retention of configuration at the phosphorus atom and full stereoselectivity of these reactions in model diastereoisomeric cis- and trans-2-phenylamino-2-thiono-4-methyl-1.3.2-dioxaphosphorinans (30) as well cis- and trans-2-phenylamino-2-seleno-4-methyl-1.3.2-dioxaphosphorinans (31) systems, are demonstrated.
- Mielniczak,Lopusiński
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p. 505 - 508
(2007/10/03)
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- Method of producing alkenylphosphine oxide or bis (alkenylphosphine oxide)
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An acetylene or diacetylene compound is reacted with a secondary phosphine oxide to produce an alkenylphosphine oxide or bis(alkenylphosphine oxide) in the presence of a palladium complex catalyst.
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- Synthesis of vinylphosphinoyl derivatives. Triethyl orthoformate as a new dehydrohalogenating agent
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Trimethyl and triethyl orthoformates are proposed as new dehydrohalogenating agents. They are used for synthesis of vinylphosphinoyl compounds.
- Kurdyumova,Ragulin,Tsvetkov
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p. 750 - 752
(2007/10/03)
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- ALKALINE HYDROLYSIS OF β AND γ-FUNCTIONAL PHOSPHONIUM SALTS
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A model study of alkaline hydrolysis of β- and γ-heterosubstituted phosphonium salts has been made and used as a synthetic method to obtain diphosphine dioxides affording additional coordination sites in an alkyl chain linked to phosphorus.After synthesis of the corresponding salts, anomalous fragmentations, such as inversion in cleavage selectivity or participation of the reaction solvent, have been pointed out in alkaline hydrolysis of β-functional phosphonium salts.A mechanism is suggested to account for the presence of all compounds detected.In the case of γ-functional phosphonium salts, the alkaline hydrolysis leads only to predicted compounds corresponding to the usual selective cleavage of one phenyl group.The results observed have been used to synthesize symmetric and asymmetric diphosphine dioxides with ether substituted side chains. - Key words: Phosphonium salt, phosphine oxide, diphosphine dioxides, alkaline hydrolysis, cleavage, mechanism.
- Cristau, Henri-Jean,Mouchet, Patrick
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p. 135 - 144
(2007/10/03)
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- Reactions of (1-Chlorovinyl)diphenylphosphine Oxide with Organometallic Reagents
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Direct substitution of 1-chlorovinyl group by an aryl or an alkyl group in the reactions of (1-chlorovinyl)diphenylphosphine oxide with aryl and alkyl Grignard reagents was observed, whereas in its reactions with the corresponding cuprates addition across the double bond constituted the dominant reaction pathway.
- Cardellicchio, Cosimo,Fiandanese, Vito,Naso, Francesco,Pietrusiewicz, K. Michal,Wisniewski, Witold
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p. 3135 - 3138
(2007/10/02)
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- Direct Synthesis of Isoxazolidinylphosphines by Cycloaddition of Nitrones to Diphenylphosphinoethenes and X-Ray Structure of 7,7-Dimethyl-1-Oxo-1-Phenyl-3-Diphenylphosphinyl-Hexahydro-1H-pyrroloOxazaphosphorine
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The 1,3-dipolar cycloaddition reaction of N-alkyl nitrones with diphenylvinylphosphines affords directly isoxazolidinylphosphines in satisfactory yields and in regio- and stereoselective manner.The parent diphenylvinylphosphine was found to favor the form
- Pietrusiewicz, K. Michal,Salamonczyk, Iwona,Wieczorek, Wanda,Brandi, Alberto,Cicchi, Stefano,Goti, Andrea
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p. 9083 - 9096
(2007/10/02)
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- Unexpected Dipolarophilic Activity of Diphenylvinylphosphine towards Nitrones
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The reactivity of diphenylvinylphosphine towards nitrones is dominated by the dipolarophilic nature of its double bond rather than by the ability of the PIII to act as an oxygen acceptor.
- Brandi, Alberto,Goti, Andrea,Pietrusiewicz, K. Michal
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p. 388 - 389
(2007/10/02)
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- Palladium-Catalysed Synthesis of Alkenyldiphenyl- and Alkenylbenzylphenylphosphine Oxides
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Alkenyldiphenyl- and Alkenylbenzylphenylphosphine oxides 3 were prepared by the palladium catalysed reaction of alkenyl bromides 1 with phosphine oxides 2a or 2b.
- Xu, Yuanyao,Xia, Jiazhi,Guo, Huiju
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p. 691 - 692
(2007/10/02)
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- SYNTHESE STEREOSELECTIVE D'ESTERS α,β-ETHYLENIQUES α-METHYLES Z OU E PAR LA REACTION DE WITTIG-HORNER A PARTIR DE PHOSPHONATES OU D'OXYDES DE PHOSPHINE
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The reaction of α-branched aldehydes with diethyl 1-carbomethoxyethyl phosphonate 1b in THF/nBuLi at low temperature leads stereoselectively to Z α-methyl α,β-unsaturated esters.From a linear aldehyde, the reaction is less stereoselective, while from α,β-unsaturated ones, the E isomers are predominantly formed in good yields.From diphenyl 1-carbomethoxyethyl phosphine oxide 2b, E α-methyl α,β-unsaturated esters are stereoselectively formed either in DMF/tBuOK or in phase transfer conditions, whatever the starting aldehyde is, also in good yields.This reagent can thus advantageously replace the corresponding P-ylid.In all cases, the reaction conditions are determined so that by-products formation is minimized.
- Etemad-Moghadam, Guita,Seyden-Penne, Jacqueline
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p. 5153 - 5166
(2007/10/02)
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- NOUVEAUX REACTIFS PRECURSEURS D' OLEFINES TRISUBSTITUEES E : LES OXYDES DE PHOSPHINE.
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From NMR data, phosphine oxides 4 show similarity to Pylids and give E trisubstituted olefins from saturated and unsaturated aldehydes.
- Seyden-Penne, J.,Etemad-Moghadam, G.,Bottin-Strzalko, T.,Simonnin, M.-P.
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p. 179 - 182
(2007/10/02)
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