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New phosphine-functionalized NHC ligands: Discovery of an effective catalyst for the room-temperature amination of aryl chlorides with primary and secondary amines

We report convenient and high-yielding syntheses of new phosphine-functionalized dihydroimidazolium salts and demonstrate their utility as ligand precursors for Buchwald-Hartwig amination. Several examples of the general formula [1-Mes-3-{2-(PR2)phenyl}imidazolidin-2-ylium][BF 4] have been prepared, where phosphines of varying steric and electronic properties (R = Ph (9), Cy (10), 1-Ad (11)) are tethered by an o-phenylene group. The synthesis was not adaptable to N-aryl groups other than mesityl, giving unexpected phosphonium salt species instead. The synthesis was adapted to flexible benzyl-linked variants of the formula [1-Ar-3-{2-(PCy 2)benzyl}imidazolidin-2-ylium][BF4], which allowed more steric variation of the dihydroimidazolium N-aryl group (Ar = Mes (21), Dipp (22)). A preliminary study of these hybrid NHC/P ligands in Buchwald-Hartwig amination catalysis (in situ precatalyst formation) revealed 11 to be the most active of the series. Premixing the isolated free NHC ligand 1-Mes-3-{2-(PAd2)phenyl}imidazolidin-2-ylidene (23) with [Pd(cinnamyl)Cl]2 provided a highly active precatalyst that performed well at room temperature and 1 mol % catalyst loading. The system was shown to have an unprecedented ability to arylate both primary alkylamines (monoarylation) and secondary dialkylamines with aryl chlorides at room temperature. Electron-rich and -poor aryl and heteroaryl halides, as well as those featuring ortho substitution, were well tolerated, while substrates featuring both primary and secondary amine groups were selectively arylated at the NH2 position. Furthermore, a preliminary examination of performance in ammonia arylation and acetone alpha-arylation showed promising results, giving good conversion and high selectivity for monoarylation in both cases.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Synthesis, X-ray structure, and physical and photophysical properties of the heterobimetallic complex Fe(eta5-C5H4PPh2) 2Pt(bph)

A chromophore-electroactive compound, Fe(eta5-C5H4PPh2) 2Pt(bph), where bph is the biphenyl dianion and Fe(eta5-C5H4PPh2)2 is 1,1?-bis(diphenylphosphino)ferrocene-P,P? has been synthesized. The single-crystal X-ray structural characteristics of this heterobimetallic complex and its disolvated methylene chloride derivative are respectively as follows: empirical formula C46H36FeP2Pt, triclinic, P1, Z = 4, a = 9.777(2) A, b = 18.003(4) A, c = 20.882(4) A, alpha = 93.57(3), beta = 100.99(3), and gamma = 90.86(3), and empirical formula C48H40Cl2FeP2Pt, monoclinic, P21/n, Z = 4, a = 12.698(3) A, b = 14.161(3) A, c = 23.376(6) A, alpha = 90, beta = 94.107(14), and gamma = 90. An electrochemical study shows that the anodic potential for the oxidation of the ferrocenyl moiety of this compound increases by +0.13 V, compared to that for Fe(eta5-C5H4PPh2)2. This change in oxidation potential agrees well with the change in energy of 0.11 eV for the dpi(Fe) ? pi*(Cp) MLCT transition upon coordination with Pt. The resultant excited state from the dpi(Pt) ? pi*(bph) MLCT transition is readily quenched by the ferrocenyl moiety unit as expected, and charge-separated redox-active centers are formed.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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The chloro-bridged dinuclear compound [{Pd[5-(COH)C6H3C(H)=N(Cy)-C2,N]}(mu-Cl)] 2(1), reacts with tertiary diphosphines in 1:1 molar ratio to give [{Pd[5-(COH)C6H3C(H)=NCy-C2,N](Cl)} 2(mu-Ph2PRPPh2)] (R: CH2, 2; CH2CH2, 3; (CH2)4, 4; (CH2) 6, 5; Fe(C5H4) 2, 6; trans-CH=CH, 7; C ? C, 8). Treatment of 1 with Ph2PCH2CH2AsPh2 (arphos) gives the dinuclear complex [{Pd[5-(COH)C6H3 C(H)=N(Cy)-C2,N](Cl)}2 (mu-Ph2PCH2C H2AsPh2)] (9). The reaction of 1 with tertiary diphosphines or arphos in 1:2 molar ratio in the presence of NH4PF6 yields the mononuclear compounds [Pd{5-(COH)C6H3C(H)=NCy-C2,N}(Ph2 PRPPh2-P,P)][PF6] (R: (CH2)4, 10; (CH2)6, 11; Fe(C5H4) 2, 12; 1,2-C6H4, 13; cis-CH=CH, 14; NH, 15) and [Pd{5-(COH)C6H3C(H)=N(Cy)-C2,N} (Ph2PCH2CH2AsPh2-P,As)][PF 6] (16). 1H-, 31P-{1H}- and 13C-{1H}-NMR, IR and mass spectroscopic data are given. The crystal structures of compounds 3, 6, 9 and 16 have been determined by X-ray crystallography.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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The carborane-selenol [(B10H11C2)SeH] has been isolated and its anion employed as a ligand. Reaction of the ligand with [AuClL] (L = PPh3, AsPh3) (1 : 1 molar ratio) or PPN[AuCl2] (PPN = N(PPh3)2) (2 : 1 molar ratio) affords the mononuclear compounds [Au(SeC2 B10H11)L] or PPN[Au(SeC2B10H11)2], respectively. Dinuclear derivatives [Au2(SeC2B10 H11)2(mu-PP)] (PP = 1,1?-bis(diphenylphosphino) ferrocene (dppf), 1,2-bis(diphenylphosphino)ethane (dppe)) are synthesised by reaction of the ligand with [Au2Cl2(mu-PP)] or by reaction of [Au(SeC2B10H11)-(AsPh3)] with the bidentate ligand. The selenolate acts in a bridging mode in [M2(mu-SeC2B10H11) (PPh3)2]X2 (M = Au, X = ClO4; M = Ag, X = TfO), obtained by treatment of the ligand with [O{Au(PPh3)}3]ClO4 or by reaction with [Ag(TfO)(PPh3)] in 1 : 2 molar ratio, respectively. The crystal structure of [Au(SeC2B10H11)(PPh3)] has been determined by X-ray diffraction studies.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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The invention relates to a can be represented by following formula (III) useful as pharmaceutical intermediates in the synthesis of pyrrole ketone compound, the method comprising: under a nitrogen atmosphere, in an organic solvent, the catalyst, organic ligand, oxidizing agent, auxiliary and presence of alkali, the following formula (I) compounds and the following formula (II) compound generating reaction, after-treatment after reaction, so as to obtain the compound of said formula (III), Wherein R is H, C 1-C 6 alkyl, C 1-C 6 alkoxy, halogen or nitro. The stated method, through through the use of catalyst, ligand, oxidizing agent, alkali and integrated reaction system of the solvent, the objective product can be obtained with high yield, in the organic synthesis in particular the technical field of pharmaceutical intermediates synthesized with good application prospect and industrialized production potential. (by machine translation)

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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A series of new heterometallic gold(I) thiolates containing ferrocenyl-phoshines were synthesized. Their antimicrobial properties were studied and compared to that of FDA-approved drug, auranofin (Ridaura), prescribed for the treatment of rheumatoid arthritis. MIC in the order of one digit micromolar were found for most of the compounds against Gram-positive bacteria Staphylococcus aureus and CA MRSA strains US300 and US400. Remarkably, auranofin inhibited S. aureus, US300 and US400 in the order of 150-300 nM. This is the first time that the potent inhibitory effect of auranofin on MRSA strains has been described. The effects of a selected heterometallic compound and auranofin were also studied in a non-tumorigenic human embryonic kidney cell line (HEK-293).

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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A catalyst don’t appear in the overall stoichiometry of the reaction it catalyzes, but it must appear in at least one of the elementary reactions in the mechanism for the catalyzed reaction. 12150-46-8, Name is 1,1-Bis(diphenylphosphino)ferrocene, molecular formula is C34H28FeP2. In a Article,once mentioned of 12150-46-8, HPLC of Formula: C34H28FeP2

Ph3PNCl (1) originates in good yield as pale yellow crystals from the reaction of Ph3PNSiMe3 with phenyliodine dichloride. According to the crystal structure analysis 1 has a monomeric molecular structure without perceptible intermolecular contacts with distances P-N of 161.0 pm, N-Cl of 175.9 pm, and with a PNCl bond angle of 110.31. 1 reacts with phosphines PR3 forming asymmetric PNP salts [Ph3PNPR3]Cl. This was tested by reactions with PEt3 and bis-diphenyl phosphano ferrocene (DPPF). The crystal structure analysis of [Ph3PNPEt3]Cl (2) shows an almost symmetric PNP bridge with distances PN of 158.6 and 157.0 pm, and with a bond angle of 145.9.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Utilization of common ligands for the ruthenium-catalyzed amination of alcohols

Simultaneous presence of bidentate phosphines with surprisingly simple structure and of the ligand triphenylphosphine were revealed as structural characteristics of new Ru catalysts for the selective conversion of primary and secondary alcohols and diols into their corresponding primary amines and diamines (see scheme). Copyright

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Application of 161265-03-8, Chemistry can be defined as the study of matter and the changes it undergoes. You’ll sometimes hear it called the central science because it is the connection between physics and all the other sciences, starting with biology.161265-03-8, Name is (9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphine), molecular formula is C39H32OP2. In a patent, introducing its new discovery.

The syntheses, characterization and photophysical properties of phosphine copper(I) and silver(I) complexes with the bispyridylpyrrolide ligand

Five mononuclear copper(I) complexes and one dinuclear silver(I) phosphine complex containing the bispyridylpyrrole ligand were synthesized and structurally characterized. Treatment of CuCl and the deprotonated bispyridylpyrrole ligand with bis(phosphine) ligands afforded the copper(I) complexes [(PDPH)Cu(XANTPhos)] (1), [(PDPH)Cu(DPEPhos)] (2), [(PDPBr)Cu(XANTPhos)] (3) and [(PDPBr)Cu(DPEPhos)] (4), while addition of two equivalences of PPh3 gave [(PDPBr)Cu(PPh3)2] (5), where PDPH- = 2,5-bis(2-pyridyl)pyrrole, PDPBr- = 2,5-bis(6?-bromo-2?-pyridyl)-pyrrole, XANTPhos = 9,9-di-methyl-4,5-bis(diphenylphosphino)xanthene, DPEPhos = oxydi-2,1-phenylene)bis-diphenylphosphine. Reaction of PDPBr- with AgOTf and DPEPhos yielded the dinuclear silver(I) complex [(PDPBr)Ag2(DPEPhos)](OTf) (6). All of these complexes were fully characterized on the basis of IR spectra, 1H and 31P NMR spectra, elements analysis, UV-Vis spectra and X-ray single crystal diffraction analysis. The photophysical properties of these complexes were also studied.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Reference of 161265-03-8, Catalysts are substances that increase the reaction rate of a chemical reaction without being consumed in the process. 161265-03-8, Name is (9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphine), molecular formula is C39H32OP2. In a Patent,once mentioned of 161265-03-8

Azabenzimidazole Compounds

The present invention is directed to compounds of formula I: or a pharmaceutically acceptable salt thereof, wherein the substituents are as defined herein.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate