2155-96-6Relevant articles and documents
Synthesis of a new type of water-soluble phosphines by addition of hydrophilic thiols to vinylphosphines. Preparation of the rhodium and palladium complexes
Paetzold, Eckhard,Michalik, Manfred,Oehme, Guenther
, p. 38 - 43 (1997)
Commercially available ω-thioalkane sodium sulfonates could easily be added to mono-, bi- and trivinylphosphines. The two-phase system became homogeneous by stirring. The products (1-6, 11) were characterized as phosphinoethyl-sulfonatoalkyl-thioethers with an unexpected high water solubility and with defined P/S ratios from 1/2, 1/4 and 1/6. All thioetherphosphines were characterized by 1H, 13C and 31P NMR spectroscopy, IR spectroscopy and elemental analysis. Addition occurs only at pH >7 and in the absence of strong electrophiles to avoid the formation of phosphonium compounds. L-Cysteine ethyl ester (8) and 2-aminoethanethiol (9) react exclusively at the thiol group. The first complexes with Pd(II), Rh(III) and Rh(I) show a participation of the thioether group in the coordination.
Synthesis of α-Aminophosphines by Copper-Catalyzed Regioselective Hydroamination of Vinylphosphines
Takata, Tatsuaki,Nishikawa, Daiki,Hirano, Koji,Miura, Masahiro
, p. 10975 - 10978 (2018)
A copper-catalyzed net hydroamination of vinylphosphine boranes with hydrosilanes and O-benzoylhydroxylamines has been developed. The reaction proceeds regioselectively to form the corresponding α-aminophosphine boranes of potent interest in medicinal and pharmaceutical chemistry. This copper catalysis is based on an umpolung, electrophilic amination strategy and provides a new electrophilic amination approach to α-aminophosphine derivatives. Additionally, although still preliminary, asymmetric synthesis has also been achieved by judicious choice of a chiral bisphosphine-ligated copper complex.
Tridentate phosphine ligands bearing aza-crown ether lariats
Pap, Levente G.,Arulsamy, Navamoney,Hulley, Elliott B.
supporting information, p. 385 - 392 (2017/11/30)
Crown ethers are useful macrocycles that act as size-selective binding sites for alkali metals. These frameworks have been incorporated into a number of macromolecular assemblies that use simple cations as reporters and/or activity triggers. Incorporating crown ethers into secondary coordination sphere ligand frameworks for transition metal chemistry will lead to new potential methods for controlling bond formation steps, and routes that couple traditional ligand frameworks with these moieties are highly desirable. Herein we report the syntheses of a family of tridentate phosphine complexes bearing tethered aza-crown ethers (lariats) designed to modularize the variation of aza-crown size, lariat length, and distal phosphine substituents, followed by the synthesis and solid-state structures of Mo(III) complexes bearing cations in the pendent crown ethers.
Direct Allylic Amination of Allylic Alcohol Catalyzed by Palladium Complex Bearing Phosphine-Borane Ligand
Hirata, Goki,Satomura, Hideaki,Kumagae, Hidenobu,Shimizu, Aika,Onodera, Gen,Kimura, Masanari
supporting information, p. 6148 - 6151 (2017/11/24)
The direct electrophilic, nucleophilic, and amphiphilic allylations of allylic alcohol by use of a palladium catalyst and organometallic reagents such as organoborane and organozinc has been developed. The phosphine-borane compound works as the effective ligand for palladium-catalyzed direct allylic amination of allylic alcohol. Thus, with secondary amines, the reaction was completed in only 1 h, even at room temperature.
Synthesis method of Josiphos chiral ferrocenyl phosphine ligands
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Paragraph 0007; 0022; 0023, (2017/05/27)
The invention discloses a synthesis method of Josiphos chiral ferrocenyl phosphine ligands, and belongs to the field of organic synthesis. The method is realized through the following steps of using ferrocene as a starting raw material; using aluminum chloride as a catalyst; taking a reaction with phosphonic chloride compound R2PCl; then, taking a reaction with vinyl diaryl phosphine under the catalysis effect of ferric trichloride and D-proline to obtain the Josiphos chiral ferrocenyl phosphine ligands. Compared with the prior art, the synthesis method has the advantages that the steps are few; the operation is simple; the production cost is reduced; the synthesis method is suitable for industrial production. The prepared Josiphos chiral ferrocenyl phosphine ligands can be used as ligands of metal catalysts for catalyzing an unsymmetrical organic reaction; the synthesis method is applied to the fields of medicine synthesis and the like.
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
Mikhailine, Alexandre A.,Maishan, Mazharul I.,Lough, Alan J.,Morris, Robert H.
supporting information; experimental part, p. 12266 - 12280 (2012/09/22)
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.
Concise syntheses of tridentate PNE ligands and their coordination chemistry with palladium(ii): A solution- and solid-state study
Anderson, Carly E.,Apperley, David C.,Batsanov, Andrei S.,Dyer, Philip W.,Howard, Judith A. K.
, p. 4134 - 4145 (2007/10/03)
A straightforward methodology for the high-yielding synthesis of the di-functionalised phosphines {Ph2P(CH2)2NC 4H8E, E = NMe (1), O (2), S (3)} via base-catalysed Michael addition is described. Reaction of the functionalised tertiary phosphines 1-3 with PdCl2(MeCN)2 affords complexes in which the ligands are bound in a tridentate fashion, namely [PdCl(κ 3-PNE)]Cl (6a, 8) as the predominant products. A κ2- PN coordination mode was also identified crystallographically for ligand 1 following its reaction with PdCl2(MeCN)2, which afforded [PdCl2(1-κ2-PN)] (6b) in ca. 5% yield. Conductivity studies of solutions of 6a are consistent with an ionic formulation, however the poor solubility of 7 and 8 precluded their study in a similar fashion. Analysis of bulk samples of [PdCl2(1)] (6) and [PdCl2(3)] (8) by 15N and 31P NMR spectroscopy in the solid state as consistent with exclusive tridentate binding of the PNE ligands. An X-ray crystallographic study has probed the coordination of 1 in the unusual salt [PdCl(1-κ3-PNN)]2[Mg(SO4) 2(OH2)4] (10) prepared by treating a methanolic solution of 6 with excess MgSO4. No data could be obtained to support the transformation of 6a into 6b on addition of excess chloride. In contrast, 6a reacts regioselectively with the water-soluble phosphine Cy 2PCH2CH2NMe3Cl to afford the cis-diphosphine complex cis-[PdCl(Cy2PCH2CH 2NMe3Cl)(1-κ2-PN)]Cl2 (9). Reaction of 1 with PdCl(Me)(COD) results in the formation of the κ2-PN dichloride complex [PdCl(Me)(1-κ2-PN)] (11). Attempts to prepare [Pd(Me)(MeCN)(1-κ2-PN)][PF 6] (12) through reaction of 11 with NaPF6 in MeCN led to decomposition. Treatment of PdMe2(TMEDA) with 1 at low temperature initially affords [PdMe2(1-κ2-NN)], which isomerises to afford [PdMe2(1-κ2-PN)] (13); at temperatures greater than 10 °C complex 13 decomposes rapidly. The Royal Society of Chemistry 2006.
Highly atom-economic one-pot formation of three different C-P bonds: General synthesis of acyclic tertiary phosphine sulfides
Baccolini, Graziano,Boga, Carla,Mazzacurati, Marzia
, p. 4774 - 4777 (2007/10/03)
The reaction of benzothiadiphosphole 1 with an equimolar mixture of R 1MgBr and R2MgBr gave intermediate A′, which, after only 4-5 min, was treated with an equimolar amount of R3MgBr, giving the asymmetric phosphine PR1R2R3 in 45% overall yield (75-80% yield when R1 = R2 and 85-90% yield when R1 = R2 = R3) and the byproduct 6 in 90% yield. The treatment of 6 with PCl3 quantitatively regenerates the starting reagent 1. Treatment of the phosphines with elemental sulfur gave the corresponding sulfides.
The synthesis and chemistry of fluorovinyl-containing phosphines and the single crystal X-ray structure of SPPr2i(CF=CF 2)
Barnes, Nicholas A.,Brisdon, Alan K.,Brown, F. R. William,Cross, Wendy I.,Crossley, Ian R.,Fish, Cheryl,Morey, James V.,Pritchard, Robin G.,Sekhri, Lakhdar
, p. 828 - 837 (2007/10/03)
The first perfluorovinyl alkyl-containing phosphines of the type PR 2(CF=CF2) (R = Et, iPr, Cy) are reported. The reactivity of these air- and moisture-stable materials has been explored, both at the phosphorus centre and at the fluorovinyl moiety. When PR 2(CX=CF2) (X = F, Cl) is reacted with LiAlH4 a mixture of PR2(CX=CFH) isomers and other defluorinated materials are produced, but the reaction with LiAlH(OBut)3 affords the single products Z-PR2(CF=CFH) or E-PR2(CCl=CFH), respectively, in high yields. Reaction of the fluorovinyl alkyl phosphines with hydrogen peroxide, elemental sulfur or selenium yields fluorovinyl-containing phosphine oxides, sulfides and selenides, respectively. The phosphine sulfide SPPr2i(CF=CF2) is the first perfluorovinyl phosphorus(v) compound to be characterised crystallographically and it exhibits an unusually short [1.9358(9) A] P=S bond. Reaction of fluorovinyl phosphines with XeF2 results in compounds of the type F 2PR2(CF=CF2), identified on the basis of multinuclear NMR studies. These compounds decompose in the presence of moisture to yield the respective phosphine oxides. Reaction of OPPh2(CF= CF2) with Br2 results in bromine addition across the double bond to give OPPh2(CFBrCF2Br).
Water Soluble Cationic Phosphine Ligands Containing m-Guanidinium Phenyl Moieties. Syntheses and Applications in Aqueous Heck Type Reactions
Hessler, Antonella,Stelzer, Othmar,Dibowski, Harald,Worm, Karin,Schmidtchen, Franz P.
, p. 2362 - 2369 (2007/10/03)
Cationic phosphine ligands containing m-guanidinium phenyl substituents {Ph3-nP[C6H4-m-NHC(NH2)(NMe 2)]n}n+ nCl- (n = 1-3) (17a-c) have been obtained by addition of dimethylcyanamide to the amino groups of tertiary (m-aminophenyl)phosphines in acidic medium. The tertiary (m-aminophenyl)phosphines Ph3-nP(C6H4-m-NH2)n (4a-c) were prepared by reaction of (3-[N,N-bis(trimethylsilyl)amino]phenyl)magnesium chloride (1) with chlorophosphines Ph3-nPCln followed by deprotection of the bis(trimethylsilyl)amino groups with methanol. Using a similar protected group synthesis as above, the secondary (m-aminophenyl)phosphine Ph(H)PC6H4-m-NH2 (7) could be prepared as well. It may be employed as a building block for the syntheses of chiral bidentate phosphine ligands (11, 14, and 15) bearing m-aminophenyl substituents. The guanidinium phosphines 17b and 17c are readily soluble in water. A comparative study of 17b and 17c, the aryl alkyl guanidinium phosphines 18 and 19, and TPPTS (P(C6H4-m-SO3Na)3) in the aqueous phase palladium-catalyzed C-C coupling reaction between p-iodobenzoate and (trifluoroacetyl)propar-gylamine shows 17b to be of surmounting activity.
