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BENZOPYRAN AND RELATED LTB4 ANTAGONISTS

The invention relates to benzopyran leukotriene B 4 (LTB. sub.4) antagonists and pharmaceutical compositions containing the compounds. The compounds inhibit the action of LTB 4 and are therefore useful in the treatment of LTB 4 induced illnesses such as inflammatory disorders.

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Reference£º
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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Unexpected substitution reactions of bis(phosphine)platinum ethene complexes

Reaction of [Pt(C2H4)(PR3)2] (R = Ph or C6H4Me-4) with moderately bulky phosphines at low temperatures did not give the expected tris- or tetrakis-phosphine complexes. Instead, mixed-phosphine complexes of the type [Pt(C2H4)(PR3)(PR?3)] (R? = C6H11, C6H4OMe-4, C6H4OMe-2, C6H4Me-4 or CH2Ph) were formed. With less bulky phosphines, chelating diphosphines or phosphites, mixed tetrakis complexes, many of them prone to disproportionation, were formed. The complexes were characterised by 31P and 195Pt NMR spectroscopy in solution.

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Reference£º
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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Fluorescence response of TICT-active aminostilbenes to copper(II) ions: Redox reaction vs ion recognition

Cu(II)-selective fluorescence enhancement (1, 2, and 4) or fluorescence quenching (3) was observed for aminostilbenes 1-4 in acetonitrile. The fluorescence responses result from efficient Cu(II)-mediated oxidation of 1-4 that forms new fluorescent species rather than from any specific noncovalent interactions. Evidence of redox reactions includes irreversible Cu(II) titration spectra, spectroscopic observation of the radical cations, and isolation of oxidized aminostilbene dimers. These results provide a new method for synthesis of tetrasubstituted tetrahydrofurans and suggest that aminostilbenes with twisted intramolecular charge-transfer activity are potential fluorescence-enhanced Cu(II) chemodosimeters. The role of Cu(II)-mediated redox reactions should be always taken into account in mechanisms for sensing of arylamine-based Cu(II)-selective fluoroionophores.

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Reference£º
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, characterization, X-ray structure and preliminary in vitro antitumor activity of the nitrosyl complex fac-[RuCl3(NO)(dppf)], dppf = 1,1?-bis(diphenylphosphine)ferrocene

The reaction of RuCl3NO ¡¤ 2H2O with stoichiometric amount of dppf, 1,1?-bis(diphenylphosphino)ferrocene, afforded the new neutral nitrosyl complex fac-[RuCl3(NO)(dppf)] which was characterized by spectroscopical, electrochemical and X-ray crystallography techniques as well as elemental analysis. The nuNO band in the IR spectrum is at 1860 cm-1 (CH2Cl2 solution) and in the cyclic voltammogram an irreversible wave was observed at -1.35 V, both are characteristics of a nitrosonium (NO+) character for the coordinated NO. Additionally, preliminary in vitro antitumor activity against the MDA-MB-231 breast tumor cell line was carried out for the new complex. The initial results indicated an important activity for fac-[RuCl3(NO)(dppf)] (IC50 = 10 ¡À 3 muM ). The complex has a higher cytotoxicity than the precursor complex RuCl3NO ¡¤ 2H2O, the free dppf ligand as well as the reference metallodrug cisplatin.

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Reference£º
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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Pt-Fe ferrocenyl compounds with hydroxyquinoline ligands show selective cytotoxicity on highly proliferative cells

Searching for a more effective chemotherapy for the treatment of Human African trypanosomiasis, the disease caused by the parasite Trypanosoma brucei, and cancer, in the current work five new [PtII(L)(dppf)](PF6) compounds, with HL = 8-hydroxyquinoline derivatives and dppf = 1,1?-bis(diphenylphosphino)ferrocene, were synthesized and fully characterized. Crystal structures of three compounds were solved by XRD. The compounds displayed fairly good activity against bloodstream T. brucei, with IC50 values in the submicromolar range (IC50: 0.14?0.93 muM), and good selectivity towards the pathogen (SI: 11 – 48) with respect to mammalian macrophages (cell line J774). Coordination to the {Pt-dppf} moiety led, in most cases, to an enhancement of the activity in respect to the bioactive ligands (11 to 41 fold). Cytotoxicity was assessed against wildtype (A2780) and cisplatin-resistance (A2780cisR) ovarian cancer cell lines. Four [PtII(L)(dppf)](PF6) compounds were more active (IC50: 1.2?4.4 muM) than cisplatin (IC50: 26.0 muM) on A2780 cells and showed far superior activity than the reference drug against A2780cisR cells. Platinum levels in A2780 cells showed poor correlation between cellular uptake and the cytotoxic activity. All the complexes interacted with DNA and the most active ones induced reactive oxygen species (ROS) formation which suggested that the mechanism of action for these complexes may be mediated by oxidative stress and interaction with DNA that could act as a potential molecular target for this type of complexes. Some complexes of this series could be considered new hits for the development of prospective agents against trypanosomatid parasites and ovarian cancer.

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Reference£º
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 and structure of [NbCl3{[NPPh2(C5H4)] 2Fe}]: The first structurally characterised complex containing a chelating di(phosphaneiminato) ligand

Reaction of [Fe{(C5H4)PPh2=NSiMe3}2] with niobium pentachloride affords the chelate complex [NbCl3{[NPPh2(C5H4)] 2Fe}].

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Reference£º
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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Bimetallic complexes supported by bis(diphenylphosphino)methane anti and syn to the Mn-Pd bonds

Redox condensation of PPN[Mn2(mu-PPh2)(CO) 8] and PdCl2(eta2-dppm) gives bimetallic PdMn(mu-PPh2)(mu-dppm)(CO)3(PPh3) (1) with an unexpected formation of PPh3. The latter can be displaced when 1 reacts with free diphosphines (dppm, dppe, dppf) giving PdMn(mu-PPh 2)(mu-dppm)(CO)3(Ph2P-X-P(=O)Ph2) (2, X=CH2 (2a), C2H4 (2b), C5H 4FeC5H4 (2c)) and [PdMn(CO)3(mu- PPh2)(mu-dppm)]2(mu-Ph2P-X-PPh 2) (3a). Complexes 2 are “A-frame”-type bimetallic complexes with an syn-dppm bridging the Mn-Pd bond. In contrast, complex 3a is a “double A-frame” anti-bridged by dppm. As a result, the latter is trans to the Mn-Pd bonds. Both types of dppm bridges are substitutionally inert. Either bridging role is best served by dppm (and not dppe or dppf). The structures of the complexes were derived from NMR analyses of all complexes and X-ray single-crystal diffraction analyses of 1, 2a and 2b. The common and stable “A-frame”-type core in these bimetallics provides a thermodynamic driving force for the opposite transmetallation migration of phosphide and phosphine (dppm) when 1 is formed.

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Reference£º
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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4-(Benzoimidazol-2-yl)-thiazole Compounds and Related Aza Derivatives

The invention relates to compounds of Formula (I) wherein ring A, X, (R1)n, R2, R3, R4, R4?, R5, n, and p are as described in the description; to pharmaceutically acceptable salts thereof, and to the use of such compounds as medicaments, especially as modulators of the CXCR3 receptor.

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Reference£º
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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Cationic and neutral (Ar-BIAN)copper(I) complexes containing phosphane and arsane ancillary ligands: Synthesis, molecular structure and catalytic behaviour in cycloaddition reactions of azides and alkynes

A series of new cationic and neutral (Ar-BIAN)copper(I) complexes [in which Ar-BIAN = bis(aryl)acenaphthenequinonediimine] was synthesised and characterised by elemental analysis, 1D and 2D NMR spectroscopy and single-crystal X-ray diffraction. The cationic complexes of the general formula [Cu(Ar-BIAN)L2]BF4 [L2 = (PPh3) 2 (1), dppe (2), dppf (3), (AsPh3)2 (4); Ar = 4-iPrC6H4 (a), 4-MeOC6H4 (b), 4-NO2C6H4 (c), 2-iPrC6H4 (d), Ph2PCH2CH2PPh2 (dppe), (Ph 2PC5H4)2Fe (dppf)] were synthesised by reaction of [Cu(EPh3)4]BF4 (E = P or As) and equimolar amounts of Ar-BIAN ligands, or by reaction of equimolar amounts of [Cu(NCMe)4]BF4, 4-iPrC6H4-BIAN (a) and diphosphanes dppe or dppf, in dichloromethane, whereas the neutral complexes of the types [CuX(Ar-BIAN)(EPh3)] [X = Cl, E = P (5); X = I, E = P (6); X = Cl, E = As (9)] and [{CuX(Ar-BIAN)}2] [X = Cl (7), I (8); Ar = a, b, c, d, 2,4,6-Me3C6H2 (e), 2,6-iPr 2C6H3 (f)] were prepared by reaction of CuCl or CuI with equimolar amounts of Ar-BIAN and EPh3 (E = P, As or Sb) in acetonitrile under reflux conditions. The type of ancillary ligand EPh 3 and the aryl substituents on Ar-BIAN play crucial roles in determining the formation of cationic or neutral copper(I) complexes. No copper(I) complexes containing coordinated SbPh3 were isolated; all the corresponding attempts led to dimeric complexes 7 or 8. Most of the complexes crystallised easily. Their study by X-ray diffraction revealed distorted-tetrahedral geometries around the copper(I) centres, which are quite influenced by the various aryl substituents on Ar-BIAN and the ancillary ligands EPh3. All complexes 1-9 except cationic dppf derivative 3a are active catalysts for cycloaddition reactions of alkynes and azides, and also show good tolerance towards functionalised substituents of alkynes and azides. Among them, the PPh3-coordinated complexes 1, 5 and 6 afforded the highest catalytic activities [turnover frequency = 26.9-45.7 h-1]. Copyright

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Reference£º
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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Phosphine complexes of tungsten(0) poly(alkyne); crystal structures of W(PhC?CPh)3(PMe3) and W(TolC?CTol)2(eta4-C4Tol 4)(PMe3)

Reactions of W(PhC?CPh)3L (L=CO or NCMe) with PMe3, PPh2Me and PPh3 produce W(PhC?CPh)3(PMe3), W(PhC?CPh)3-(PPh2Me) and W(PhC?CPh)3(PPh3), respectively. Reaction of W(PhC?CPh)3(NCMe) with 1,1?-bis(diphenylphosphino)ferrocene (dppf) forms W(PhC?CPh )3(eta1-dppf) and [W(PhC?CPh)3J2(eta1, eta1-dppf). Treating W(RC?CR)2(eta4-C4R4)(NCMe) (R = Ph and Tol) with PMe3 affords W(RC?CR)2(eta4-C4R4) (PMe3). W(PhC?CPh)3(PMe3) crystallizes in the space group P3 with a=14.000(4), c=11.183(3) A, V=1898.3(7) A3, Z=2 and RF=0.032. W(TolC?CTol)2(eta4-C4Tol 4)(PMe3) crystallizes in the space group P21/c with a=13.588(2), b=19.289(5), c=22.150(5) A, beta=90.57(2), V=5805.(2) A3, Z=4 and RF=0.055.

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Reference£º
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