57137-53-8Relevant academic research and scientific papers
Direct and straightforward transfer of C1 functionalized synthons to phosphorous electrophiles for accessinggem-P-containing methanes
Touqeer, Saad,Ielo, Laura,Miele, Margherita,Urban, Ernst,Holzer, Wolfgang,Pace, Vittorio
supporting information, p. 2425 - 2429 (2021/04/02)
The direct transfer of different α-substituted methyllithium reagents to chlorinated phosphorous electrophiles of diverse oxidation state (phosphates, phosphine oxides and phosphines) is proposed as an effective strategy to synthesize geminal P-containing
Ethylene selective oligomerization catalyst systems and method for ethylene oligomerization using the same
-
, (2019/04/25)
The disclosure provides a catalyst system and a method for ethylene oligomerization using this. The catalyst system contains: ligand a, containing carbene groups of imidazole ring type; transition metal compound b, that is one of IVB?VIII group metal comp
Intramolecular exchange of coordinated and dangling phosphine groups in pentacarbonyl[(diphenylphosphino)(di-p-tolylphosphino)methane]tungsten(0)
Keiter, Richard L.,Chen, Deliang,Holloway, Geoffrey A.,Keiter, Ellen A.,Zang, Yi,Huml, M. Todd,Filley, Jonathan,Brandt, Douglas E.
scheme or table, p. 4619 - 4622 (2012/07/27)
Equilibrium constants and rates have been determined for the isomerization of the linkage isomers (OC)5W[κ1-PPh 2CH2P(p-tolyl)2] (5) and (OC) 5W[κ1-P(p-tolyl)2CH2PPh 2] (6). It is proposed that this intramolecular exchange involves a nucleophilic attack of the pendant phosphine on a cis carbonyl group, followed by ring opening and a 1,2-shift.
Synthesis and structure of intermediates in copper-catalyzed alkylation of diphenylphosphine
Cain, Matthew F.,Hughes, Russell P.,Glueck, David S.,Golen, James A.,Moore, Curtis E.,Rheingold, Arnold L.
experimental part, p. 7650 - 7662 (2010/11/19)
Cu(I) catalysts for alkylation of diphenylphosphine were developed. Treatment of [Cu(NCMe)4][PF6] (1) with chelating ligands gave [CuL(NCMe)][PF6] (2; L = MeC(CH2PPh2) 3 (triphos), 3; L = 9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene (XantPhos)). These complexes catalyzed the alkylation of PHPh2 with PhCH2Br in the presence of the base NaOSiMe3 to yield PPh2CH2Ph (4). The precursors Cu(dtbp)(X) (dtbp =2,9-di-t-butylphenanthroline, X = Cl (5) or OTf (6)), CuCl, and 1 also catalyzed this reaction, but dtbp dissociated from 5 and 6 during catalysis. Both 2 and 3 also catalyzed alkylation of PHPh2 with PhCH 2Cl/NaOSiMe3, but XantPhos dissociation was observed when 3 was used. When CH2Cl2 was used as the solvent for alkylation of PhCH2Cl with precursors 2 or 3, or of PhCH(Me)Br with 2, it was competitively alkylated to yield PPh2CH2Cl (7), which was formed exclusively using 2 in the absence of a benzyl halide. Cu(triphos)-catalyzed alkylation of PhCH(Me)Br gave mostly PPh2CHMePh (8), along with some Ph2P-PPh2 (9), which was also formed in attempted alkylation of dibromoethane with this catalyst. The phosphine complexes [Cu(triphos)(L′)][PF6] (L′ = PH2Ph (10), PH2CH2Fc (Fc = C5H4FeC 5H5, 11), PHPh2 (12), PHEt2 (13), PHCy2 (Cy = cyclo-C6H11, 14), PHMe(Is) (Is = 2,4,6-(i-Pr)3C6H2, 15), PPh2CH 2Ph (16), PPh2CH2Cl (17)), and [Cu(XantPhos)(L′)][PF6] (L′ = PHPh2 (18), PPh2CH2Ph (19)) were prepared by treatment of 2 and 3 with appropriate ligands. Similarly, treatment of dtbp complexes 5 or 6 with PHPh2 gave [Cu(dtbp)(PHPh2)(X)] (X = OTf (20a) or Cl (20b)), and reaction of PPh2CH2Ph (4) with 1 formed [Cu(PPh2CH2Ph)3][PF6] (21). Complexes 2, 3, 11-14, 16, 17, 19, and 21 were structurally characterized by X-ray crystallography. Deprotonation of diphenylphosphine complex 12 in the presence of benzyl bromide gave diphenylbenzylphosphine complex 16, while deprotonation of 12 in CD2Cl2 gave 17 containing a PPh2CD2Cl ligand. Low-temperature deprotonation of the soluble salt 12-[B(ArF)4] (ArF = 3,5-(CF 3)2C6H3) in THF-d8 gave the phosphido complex Cu(triphos)(PPh2) (22). Thermally unstable 22 was characterized by NMR spectroscopy and, in comparison to 12, by density functional theory (DFT) calculations, which showed it contained a polarized Cu-P bond. The ligand substitution step required for catalytic turnover was observed on treatment of 16 or 17 with PHPh2 to yield equilibrium mixtures containing 12 and the tertiary phosphines 4 or 7; equilibrium constants for these reactions were 8(2) and 7(2), favoring complexation of the smaller secondary phosphine in both cases. These observations are consistent with a proposed mechanism for catalytic P-C bond formation involving deprotonation of the cationic diphenylphosphine complex [Cu(triphos)(PHPh2)][PF 6] (12) by NaOSiMe3 to yield the phosphido complex Cu(triphos)(PPh2) (22). Nucleophilic attack on the substrate (benzyl halide or CH2Cl2) then yields the tertiary phosphine complex [Cu(triphos)(PPh2CH2X)][PF6] (X = Ph (16) or Cl (17)), and ligand substitution with PHPh2 regenerates 12.
Bisphosphine-functionalized cyclic decapeptides based on the natural product gramicidin s: A potential scaffold for transition-metal coordination
Burck, Sebastian,Van Assema, Sander G. A.,Lastdrager, Bas,Slootweg, J. Chris,Ehlers, Andreas W.,Otero, Jose M.,Dacunha-Marinho, Bruno,Llamas-Saiz, Antonio L.,Overhand, Mark,Van Raaij, Mark J.,Lammertsma, Koop
experimental part, p. 8134 - 8145 (2011/03/20)
The natural product Gramicidin S is a promising scaffold for novel oligopeptide-based bisphosphine ligands, combining the advantageous rigid chiral backbone with the close proximity of phosphine substituents. The required unnatural, phosphine-containing,
Mild synthesis of organophosphorus compounds: Reaction of phosphorus-containing carbenoids with organoboranes
Antczak, Monika I.,Montchamp, Jean-Luc
supporting information; experimental part, p. 977 - 980 (2009/04/10)
Organoboranes react with phosphorus-containing carbenoids to produce a variety of functionalized organophosphorus compounds under mild conditions. In some cases, selective migration of one group atached to boron can be observed. Phosphonite-borane complexes are introduced as novel synthons for the synthesis of phosphinic esters.
Phosphorus-carbon bond formation catalysed by electrophilic N-heterocyclic phosphines
Burck, Sebastian,Foerster, Daniela,Gudat, Dietrich
, p. 2810 - 2812 (2008/09/19)
A P-chloro-diazaphospholene catalyses the phosphorus-carbon bond formation reaction between diphenylsilylphosphine and various alkyl chlorides. The Royal Society of Chemistry 2006.
Diphosphanes with polarized and highly reactive P-P bonds
Burck, Sebastian,Gudat, Dietrich,Nieger, Martin
, p. 4801 - 4804 (2007/10/03)
Uneven split: The combination of a stable cationic diazaphospholenium with stable anionic diphenylphosphanyl or phospholyl fragments affords diphosphanes with a polarized P-P bond (see scheme). This results not only in interesting molecular structures, but also in the chemical activation of the P-P bond in addition reactions.
Bridged 1-methylbisimidazoles as building blocks for mixed donor bi- and tridentate chelating ligands
Braussaud,Rüther,Cavell,Skelton,White
, p. 626 - 632 (2007/10/03)
Novel bi- and tridentate imidazole chelate ligands consisting of varying donor sets were prepared using an efficient one- or two-step procedure. Keto- and methylene-bridged bisimidazoles 1, 2 served as versatile starting materials for the introduction of additional donor groups, thus allowing the facile variation of donor sets within a bisimidazole ligand framework.
Synthese von Ph2P-CH2-PH2 und (Ph2P-CH2)2PH durch Phosphinomethylierung von PH3 unter Phasentransferkatalyse
Langhans, Klaus-Peter,Stelzer, Othmar,Weferling, Norbert
, p. 995 - 999 (2007/10/02)
Linear Oligophosphaalkanes, XXV. - Synthesis of Ph2P-CH2-PH2 and (Ph2P-CH2)2PH by Phosphinomethylation of PH3 with Phase-Transfer Catalysis Alkylation of Ph2PH with CH2Cl2 und phase-transfer conditions in the system dichloromethane/toluene/water affords P
