6361-05-3Relevant academic research and scientific papers
Synthesis of tertiary phosphine oxides by alkaline hydrolysis of quaternary phosphonium zwitterions using excess t-BuOK and stoichiometric water
Zhong, Chun-Hong,Huang, Wenhua
supporting information, p. 1537 - 1546 (2021/01/07)
Hydrolysis of quaternary arylphosphonium zwitterions bearing COO? and those in situ generated from the corresponding salts bearing Ac or OH at the aryl ring by using excess t-BuOK and stoichiometric water affords tertiary arylphosphine oxides in moderate to excellent yield, in contrast to hydrolysis of these zwittertion or salts in aqueous NaOH that mainly provides phosphine oxides with the loss of the aryl group. Under the t-BuOK/water conditions, hydrolysis of carbonyl stabilized ylides Ph3P = CHCOR (R = Ph, Me, and OEt), which partially exist as phosphonium enolates, prefers to produce Ph2P(O)CH2COR. Further reduction of Ph2P(O)CH2COMe by PhSiH3 allows the preparation of Ph2PCH2COMe in 43% yield.
New Tridentate Carbamoylmethylphosphine Oxides: Synthesis and NMR Spectra
Bondarenko,Belus’,Artyushin,Peregudov
, p. 2273 - 2280 (2021/02/12)
Abstract: Amidation of diphenylphosphorylacetic acid gave tridentate ligands Ph2P(O)CH2CON(R)· CH2CH2P(O)Ph2 (R = Me, Bu, Oct) containing a phosphoryl group in the amide moiety. According to the
Copper-Catalyzed Decarboxylative Hydrophosphinylation of α-Acyl-α-Diazoacetates
Zhang, Can,Dong, Chao,Wang, Xin,Shen, Ruwei
supporting information, p. 7440 - 7444 (2020/12/01)
A simple copper-catalyzed decarboxylation–denitrogenation C–P coupling reaction of α-acyl-α-diazoacetates with hydrophosphoryl compounds is reported. The reaction may proceed via a process involving the generation of (diazomethyl)ketones after hydrolysis in the presence of water and the hydrophosphinylation of the copper carbene intermediates. This finding may suggest the potential use of the relatively more readily available α-acyl-α-diazoacetates as replacement of (diazomethyl)ketones in some cases.
Palladium-catalyzed C(sp3)–P(III) bond formation reaction with acylphosphines as phosphorus source
Zhang, Mengyue,Ma, Zhichao,Du, Hongguang,Wang, Zhiqian
, (2020/06/29)
Palladium-catalyzed C(sp3)–P(III) bond formation reaction for alkyl substituted phosphines preparation was developed. In this reaction, various alkyl bromides and limited alkyl chlorides reacted with acylphosphine under relative mild and easily accessible condition, and differential phosphines were afforded in good yields. This reaction made up the application of palladium catalysis in C(sp3)–P(III) bond formation, and indicated a practical application of acylphosphine as a phosphination reagent.
Adaptive Behavior of a Ditopic Phosphine Ligand
Renard, Nicolas,Brenner, Eric,Matt, Dominique,Gourlaouen, Christophe
, p. 2996 - 3004 (2019/07/05)
Synthetic, structural and computational studies have been performed to investigate ligand interchange in the fluxional chelate complex [RhCl3{Ph2PACH2C(OA)OEt-κ2POA}{Ph2PBCH2C(OB)OEt-κP}], which contains two hybrid phosphine-ester ligands, one acting as P,O chelator, the other as a P-monodentate ligand. The observed ligand exchange may occur according to two pathways which both involve four elementary movements: a) oxygen dissociation with formation of a lacunary octahedral RhCl3P2 intermediate; b) migration of the Cl atom trans to PA towards the position trans to PB; c) rotations of the phosphine moieties about the Rh–P bonds, these occurring either concomitantly with the Cl displacement or in a separate step; d) coordination of an oxygen atom of the second phosphine. The two pathways thus differ by conformational changes within two distinct steps. In each pathway the rate-limiting step is the one involving a movement of the two phosphines, which generates steric frictions between the two PPh2 groups. The calculated theoretical energetic spans of both pathways (ΔG≠ ≈ 17 kcal mol–1) is close to the energy barrier obtained from a variable temperature NMR study carried out in C2D2Cl4 (ΔG≠ = 15.5 kcal mol–1). While one of the pathways leads to an isomer with a Rh-bound ethoxy O atom, the other results in the isomer having the metal coordinated to the adjacent C=O group. Exchange between the two O atoms of the coordinated ester group occurs readily (ΔGTS = 12.5 kcal mol–1).
Reaction of (2-methoxyprop-2-yl)diphenylphosphine oxide with alkyl bromides
Morgalyuk, Vasilii P.,Strelkova, Tatyana V.,Kagramanov, Nikolai D.,Artem'ev, Alexander V.,Brel, Valery K.
, p. 290 - 291 (2018/06/01)
Treatment of (2-methoxyprop-2-yl)diphenylphosphine oxide with alkyl bromides affords alkyl(diphenyl)phosphine oxides in good yields.
New synthesis of trimethylsilyl diphenylphosphinite
Morgalyuk, Vasily P.,Strelkova, Tat'yana V.,Nifant'ev, Eduard E.,Brel, Valery K.
, p. 397 - 398 (2016/10/05)
Treatment of (2-hydroxyprop-2-yl)diphenylphosphine oxide with silylating agents affords trimethylsilyl diphenylphos-phinite in high yield.
Photocatalytic ?±-oxyamination of stable enolates, silyl enol ethers, and 2-oxoalkane phosphonic esters
Schroll, Peter,K??nig, Burkhard
supporting information, p. 309 - 313 (2015/03/03)
Fast ?±-oxyamination of stable enolates, silyl enol ethers, and in situ deprotonated dialkyl 2-oxoalkane phosphonates and diphenyl-2-oxoalkyl phosphine oxides was performed in the presence of [Ru(bpy)3]2+ (bpy = 2,2a?2-bipyridyl) as a photocatalyst, 2,2,6,6-tetramethylpiperidine nitroxide (TEMPO), and visible light. The key step was the light-induced one-electron oxidation of TEMPO into the 2,2,6,6-tetramethylpiperidine- 1-oxoammonium ion, which was nucleophilically attacked to yield ?±-functionalized carbonyl compounds. The reaction time was significantly reduced by the use of the microreactor flow technique.
Sequestration, fluorometric detection, and mass spectroscopy analysis of lanthanide ions using surface modified magnetic microspheres for microfluidic manipulation
Shkrob, Ilya A.,Kaminski, Michael D.,Mertz, Carol J.,Rickert, Paul G.,Derzon, Mark S.,Rahimian, Kamyar
supporting information; experimental part, p. 15705 - 15710 (2010/01/30)
Several methods for rapid sequestration, fluorometric detection, and the subsequent mass spectroscopic analysis of lanthanide ions using surface modified polystyrene magnetic microspheres are demonstrated. Mixed-ligand antenna complexes of Eu3+ in which one of the ligands is attached to the surface of the microspheres have been used as a means for the sequestration, immobilization, and detection of these ions. Using the ion-exchange properties of these microspheres, this scheme has been extended to the detection of nonluminescent ions. The principles of these assays form the basis for operation of a portable microfluidic device for general analytical and nuclear forensics applications and indicate the manner in which the established methods of analytical chemistry, such as liquid-liquid extraction and ion-exchange chromatography, can be adapted for such miniature devices.
Advantages of organophosphorus synthesis in ionic liquids: "Green" approaches to useful phosphorus-substituted building blocks
Odinets,Matveeva,Sharova,Artyushin,Kozlov,Vorob'eva,Osipov,Roeschenthaler
scheme or table, p. 383 - 388 (2009/04/04)
Novel examples concerning the application of ionic liquids as a promoting reaction media in organophosphorus chemistry are discussed. Imidazolium ionic liquids were found to accelerate the Michaelis-Arbuzov reaction allowing to perform it under very mild conditions. Both phosphonium and imidazolium ILs give the possibility to perform easily direct amidation of phosphoryl acetic acids by various amines. Nucleophilic displacement reactionin a series of bromoalkylphosphonates was carried out in quantitative yield to afford azidoalkylphosphonates using the [bmim][PF6]/H2O system. Copyright Taylor & Francis Group, LLC.
