829-85-6Relevant articles and documents
Reaction of secondary phosphine chalcogenides with diallylamine
Verkhoturova,Kazantseva,Arbuzova,Albanov,Gusarova,Trofimov
, (2014)
Diphenyl- or bis(2-phenylethyl)phosphine sulfides and -phosphine selenides react with diallylamine under radical initiation (UV or AIBN) to afford the corresponding diadducts and tetrahydropyrrolylmethyl phosphine chalcogenides. The yield and the ratio of
Indium(III) promoted oxidative P-P coupling of silylphosphines
Cartlidge, Ashleigh J.,Matthews, Peter D.
supporting information, (2022/01/28)
The reaction of indium(III) salts with Ph2PSiMe3 and PhP(SiMe3)2 gives rise to a one- and two-electron reductive P-P coupling respectively, with the formation of new P-P bonds resulting in the preparation of (Ph2P)2 and the cyclicoligophosphane compounds (PhP)4 and (PhP)6.
Reversing Lewis acidity from bismuth to antimony
Balasubramaniam, Selvakumar,Jemmis, Eluvathingal D.,Kumar, Sandeep,Sharma, Deepti,Venugopal, Ajay
supporting information, p. 8889 - 8892 (2021/09/10)
Investigations on the boundaries between the neutral and cationic models of (Mesityl)2EX (E = Sb, Bi and X = Cl?, OTf?) have facilitated reversing the Lewis acidity from bismuth to antimony. We use this concept to demonstrate a higher efficiency of (Mesityl)2SbOTf(Mesityl)2BiOTf in the catalytic reduction of phosphine oxides to phosphines. The experiments supported with computations described herein will find use in designing new Lewis acids relevant to catalysis.
Process for preparation of phosphorane and phosphonyl compounds
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Paragraph 0031-0033, (2021/06/06)
The invention relates to the field of new materials of fine chemicals, in particular to a new safe, convenient, mild, efficient, environment-friendly and economical preparation process technology of phosphorane and phosphonyl compounds.
Phosphirenium ions as masked phosphenium Catalysts: Mechanistic evaluation and application in synthesis
Gasperini, Danila,Neale, Samuel E.,Mahon, Mary F.,MacGregor, Stuart A.,Webster, Ruth L.
, p. 5452 - 5462 (2021/06/01)
The utilization of phosphirenium ions is presented; optimized and broadened three-membered ring construction is described together with the use of these ions as efficient pre-catalysts for metal-free carbonyl reduction with silanes. Full characterization of the phosphirenium ions is presented, and initial experimental and computational mechanistic studies indicate that these act as a "masked phosphenium"source that is accessed via ring opening. Catalysis proceeds via associative transfer of {Ph2P+} to a carbonyl nucleophile, Ha'SiR3 bond addition over the C=O group, and associative displacement of the product by a further equivalent of the carbonyl substrate, which completes the catalytic cycle. A competing off-cycle process leading to vinyl phosphine formation is detailed for the hydrosilylation of benzophenone for which an inverse order in [silane] is observed. Experimentally, the formation of side products, including off-cycle vinyl phosphine, is favored by electrondonating substituents on the phosphirenium cation, while catalytic hydrosilylation is promoted by electron-withdrawing substituents. These observations are rationalized in parallel computational studies.
The Trityl-Cation Mediated Phosphine Oxides Reduction
Landais, Yannick,Laye, Claire,Lusseau, Jonathan,Robert, Frédéric
supporting information, p. 3035 - 3043 (2021/05/10)
Reduction of phosphine oxides into the corresponding phosphines using PhSiH3 as a reducing agent and Ph3C+[B(C6F5)4]? as an initiator is described. The process is highly efficient, reducing a broad range of secondary and tertiary alkyl and arylphosphines, bearing various functional groups in generally good yields. The reaction is believed to proceed through the generation of a silyl cation, which reaction with the phosphine oxide provides a phosphonium salt, further reduced by the silane to afford the desired phosphine along with siloxanes. (Figure presented.).
2-Phenoxyethyldiphenylphosphine oxide as an equivalent of diphenylvinylphosphine oxide in nucleophilic additions
Bondarenko, Natalia A.,Tcarkova, Kseniia V.,Belus', Svetlana K.,Artyushin, Oleg I.
, p. 902 - 910 (2021/06/25)
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.
Photocatalytic Arylation of P4 and PH3: Reaction Development Through Mechanistic Insight
Cammarata, Jose,Gschwind, Ruth M.,Lennert, Ulrich,Rothfelder, Robin,Scott, Daniel J.,Streitferdt, Verena,Wolf, Robert,Zeitler, Kirsten
supporting information, p. 24650 - 24658 (2021/10/14)
Detailed 31P{1H} NMR spectroscopic investigations provide deeper insight into the complex, multi-step mechanisms involved in the recently reported photocatalytic arylation of white phosphorus (P4). Specifically, these studies have identified a number of previously unrecognized side products, which arise from an unexpected non-innocent behavior of the commonly employed terminal reductant Et3N. The different rate of formation of these products explains discrepancies in the performance of the two most effective catalysts, [Ir(dtbbpy)(ppy)2][PF6] (dtbbpy=4,4′-di-tert-butyl-2,2′-bipyridine) and 3DPAFIPN. Inspired by the observation of PH3 as a minor intermediate, we have developed the first catalytic procedure for the arylation of this key industrial compound. Similar to P4 arylation, this method affords valuable triarylphosphines or tetraarylphosphonium salts depending on the steric profile of the aryl substituents.
One-pot synthesis of binaphthyl-based phosphines via direct modification of BINAP
Ye, Jing-Jing,Zhang, Jian-Qiu,Shimada, Shigeru,Han, Li-Biao
supporting information, (2021/11/18)
Herein reported is the convenient and efficient strategy for the preparation of binaphthyl-based phosphines through direct modification to the commercially available 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (BINAP) with sodium. In the absence of 15-crown-5-ether, a cyclic sodium dinapthylphospholide intermediate is mainly generated. With 15-crown-5-ether, P-Ph bonds are selectively cleft by Na to produce binaphthyl-based disodium phosphides. The mechanism of selective formation of sodium dinapthylphospholide or binaphthyl-based disodium phosphides is proposed.
Mild intramolecular P–C(sp3) bond cleavage in bridging diphosphine complexes of RuII RhIII and IrIII
De'Ath, Peter,Elsegood, Mark R.J.,Halliwell, Christopher A.G.,Smith, Martin B.
, (2021/02/21)
Three new carboxylic acid functionalised diphosphines, R2PCH2N(Ar)CH2PR2 [CyL1 R = Cy, Ar = (1-CO2H)(3-OMe)C6H3, CyL2 R = Cy, Ar = (1-CO2H)(3-OH)C6H3 and PhL3 R = Ph, Ar = (1-CO2H)(5-OMe)C6H3] have been prepared from condensation of R2PCH2OH and the appropriate aromatic amine in MeOH, and isolated as colourless solids (for CyL1, CyL2) in good yield. Reaction of CyL1, CyL2, or PhL3, along with the previously reported diphosphines PhL1, PhL2, and PhL4, and [RuCl(μ-Cl)(η6-Me2CHC6H4Me)]2 in CH2Cl2 affords the P/P-bridging dinuclear ruthenium(II) complexes {RuCl2(η6-Me2CHC6H4Me)}2(μ-CyL1?PhL4) 1a?f as red/orange solids. Careful monitoring by 31P{1H} NMR spectroscopy of CDCl3 solutions of 1a?e revealed remarkably clean P?Csp3 bond cleavage to give RuII mononuclear species 2a?e and the known secondary phosphine complexes RuCl2(η6-Me2CHC6H4Me)(PCy2H) 3 and RuCl2(η6-Me2CHC6H4Me)(PPh2H) 4. Furthermore, facile P?Csp3 bond cleavage of PhL1 can be observed using the chloro-bridged dimers [IrCl(μ-Cl)(η5-C5Me5)]2 or [RhCl(μ-Cl)(η5-C5Me5)]2 instead. Deuterium labelling of CyL1, CyL1, PhL1, and PhL2 enabled the assignment of the methylene protons to be confirmed from 1H NMR spectroscopy. All new compounds have been characterised using a range of spectroscopic and analytical techniques. Single crystal X-ray structures have been determined for CyL1, 1d·3OEt2, 1f·2CDCl3·OEt2, 2b, 2c, 2d·CDCl3, 2e·0.5OEt2 and 6b·1.5CDCl3. The free phenolic group in CyL1, 1d·3OEt2, 1f·2CDCl3·OEt2, 2b and 2d·CDCl3 participates in intra- or intermolecular O?H···O hydrogen bonding.
