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(Tetramethylthiophene)ruthenium Dichloride Dimer: A Versatile Synthetic Intermediate in Thiophene Coordination Chemistry

The thermal reaction of <(cymene)RuCl2>2 and tetramethylthiophene gives <(TMT)RuCl2>2 (1).Treatment of 1 with silver salts in the presence of various ligands gives salts of <(TMT)RuL3>(2+) where L3=(H2O)3, (CH3CN)3, and TMT.A crystallographic study demonstrated that <(TMT)2Ru>(BF4)2*2CH3NO2 adopts a sandwich structure with sulfur atoms sited cis on the pseudooctahedron.Cyclic voltammetry studies show that <(TMT)2Ru>(2+) undergoes two reversible one-electron reductions.Solutions of 1 and phosphine and amine donors react to give well-behaved monometallic derivatives of the type (TMT)RuCl2L where L is PPr3 and NH2C6H4Me.For bulky L=PPh3 and P(C6H4Me)3, variable-temperature NMR studies demonstrate hindered rotation about the Ru-P and Ru…TMT axes.Treatment of 1 with (Me3Si)2S gives the cluster <(TMT)RuCl>3S(1+) whose PF6(1-) salt was examined by X-ray crystallography.The cluster is comprised of three conjoined pseudooctahedral Ru centers bridged by one mu3-S and three mu-Cl atoms.

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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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Catalytic Asymmetric Chlorocyclization of 2-Vinylphenylcarbamates for Synthesis of 1,4-Dihydro-2H-3,1-benzoxazin-2-one Derivatives

A facile synthetic approach to a series of chiral 4-chloromethyl-1,4-dihydro-2H-3,1-benzoxazin-2-one derivatives has been described. This transformation is achieved through the catalytic asymmetric chlorocyclization of 2-vinylphenylcarbamates using a newly developed organocatalyst. Furthermore, the resulting products can be easily converted into diverse bioactive agents.

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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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The reaction rate of a catalyzed reaction is faster than the reaction rate of the uncatalyzed reaction at the same temperature.15929-43-8, Name is Bis(4-(trifluoromethyl)phenyl)phosphine oxide, molecular formula is C14H9F6OP. In a Article£¬once mentioned of 15929-43-8, Recommanded Product: 15929-43-8

A versatile synthesis of chiral beta-aminophosphines

A method for the preparation of chiral beta-aminophosphines having substituted P-aryl groups is described. Ring-opening of cyclic sulfamidates with metal diarylphosphinites yields beta-aminophosphine oxides, which are then reduced to the corresponding phosphines. Effects of the diarylphosphinite countercation on the regioselectivity of the ring-opening reaction (P- versus O-alkylation) are discussed. This method enables the introduction of electron-deficient, electron-rich and sterically hindered diarylphosphino groups, as demonstrated by the synthesis of a series of novel, P-aryl-substituted beta-aminophosphines derived from tert-leucinol, valinol and phenylglycinol. Access to these derivatives will create new opportunities for steric and electronic tuning of beta-aminophosphine-derived chiral ligands and organocatalysts.

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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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Catalytic Asymmetric Chlorocyclization of 2-Vinylphenylcarbamates for Synthesis of 1,4-Dihydro-2H-3,1-benzoxazin-2-one Derivatives

A facile synthetic approach to a series of chiral 4-chloromethyl-1,4-dihydro-2H-3,1-benzoxazin-2-one derivatives has been described. This transformation is achieved through the catalytic asymmetric chlorocyclization of 2-vinylphenylcarbamates using a newly developed organocatalyst. Furthermore, the resulting products can be easily converted into diverse bioactive agents.

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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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The reaction rate of a catalyzed reaction is faster than the reaction rate of the uncatalyzed reaction at the same temperature.15929-43-8, Name is Bis(4-(trifluoromethyl)phenyl)phosphine oxide, molecular formula is C14H9F6OP. In a Article£¬once mentioned of 15929-43-8, 15929-43-8

A versatile synthesis of chiral beta-aminophosphines

A method for the preparation of chiral beta-aminophosphines having substituted P-aryl groups is described. Ring-opening of cyclic sulfamidates with metal diarylphosphinites yields beta-aminophosphine oxides, which are then reduced to the corresponding phosphines. Effects of the diarylphosphinite countercation on the regioselectivity of the ring-opening reaction (P- versus O-alkylation) are discussed. This method enables the introduction of electron-deficient, electron-rich and sterically hindered diarylphosphino groups, as demonstrated by the synthesis of a series of novel, P-aryl-substituted beta-aminophosphines derived from tert-leucinol, valinol and phenylglycinol. Access to these derivatives will create new opportunities for steric and electronic tuning of beta-aminophosphine-derived chiral ligands and organocatalysts.

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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

Discovery of 2-(Diphenylphosphino)benzoic acid

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beta-amino alcohol derived beta-hydroxy- and beta-(o- diphenylphosphino)benzoyloxy(o-diphenylphosphino)benzamides: An ester-amide ligand structural model for the palladium-catalyzed allylic alkylation reaction

(Chemical Equation Presented) A commercially available collection of beta-amino alcohols have been converted to their corresponding beta-hydroxy- and beta-(o-diphenylphosphino)benzoyloxy(o-diphenylphosphino)benzamides 11a-f and 12a-f and have been employed in the Tsuji-Trost asymmetric alkylation reaction with 1,3-diphenylpropenyl acetate. With the exception of ligands 11b and 11f, the beta-hydroxybenzoyloxy (o-diphenylphosphino)benzamide ligands 11a-f primarily afforded the (R)-enantiomer of the product. In contrast, the bis(phosphine) ligands 12a-f consistently afforded the (S)-enantiomer. The best ligand (12c) was derived from cis-(1R,2S)-2-amino-1,2-diphenyl-1-ethanol, and when applied in the asymmetric allylic alkylation reaction, it yielded the product in an enantiomeric ratio of 97.8.22 favoring the (S)-enantiomer. A computational study was conducted on the conformation that this ligand might adopt in the palladium-catalyzed alkylation reaction as compared to that of the Trost ligand 1a. 2009 American Chemical Society.

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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, crystal structure, antibacterial, cytotoxic, and anticancer activities of new Pd(II) complexes of tri-p-tolyl phosphine with thiones

Four Pd(II) complexes of general formula [Pd(L1)2(L2)2], where L1 = pyridine-2(1H)-thione, pyrimidine-2(1H)-thione, pyridine-4(1H)-thione, and pyridine-4(1H)-thione, L2 = tri-p-tolylphosphine, have been synthesized by direct reaction of K2[PdCl4] with phosphine and heterocyclic thiones ligands in 1 : 2 : 2 molar ratio. The complexes have been characterized by elemental analyses, FT-IR and multinuclear NMR spectroscopy. The complexes 1 and 2 were also characterized by single crystal X-ray diffraction which revealed that the Pd(II) atom adopted a nearly square planar geometry with two tri-p-tolyphosphine molecules bound in a trans fashion and also two pyridine-2(1H)-thione (1) or pyrimidine-2(1H)-thione (2) molecules trans to each other. The compounds were tested for antibacterial activity, DNA interaction by brine shrimp lethality bioassay, antitumor activity, and gel electrophoresis. The complexes demonstrated moderate activity against gram positive and gram negative bacterial strains in comparison with a standard drug imipenum. Their antitumor activity against MCF7 tumor cell line was determined to be comparable to that of doxorubicin. The investigated compounds demonstrated no cytotoxic effect in brine shrimp bioassay study.

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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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The reaction rate of a catalyzed reaction is faster than the reaction rate of the uncatalyzed reaction at the same temperature.213697-53-1, Name is 2′-(Dicyclohexylphosphino)-N,N-dimethyl-[1,1′-biphenyl]-2-amine, molecular formula is C26H36NP. In a Patent, authors is Wei-Bo, Wang£¬once mentioned of 213697-53-1, 213697-53-1

Substituted phenyl farnesyltransferase inhibitors

Compounds of formula (I) 1or pharmaceutically acceptable salts thereof, inhibit farnesyltransferase. Methods for making the compounds, pharmaceutical compositions containing the compounds, and methods of treatment using the compounds are disclosed.

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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

Extracurricular laboratory:new discovery of 2-(Diphenylphosphino)benzoic acid

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Directed branched-regioselective hydroformylation of 2-substituted allylic o-DPPB esters

Branched-regioselective hydroformylation of allylic o-DPPB esters has been accomplished with mono- and disubstituted alkene functions in good to excellent yields and selectivities. Optimized reaction conditions allowed the reaction of even trisubstitued alkenic functions. These reactions occur as a result of a significant rate-accelerating effect exerted by the catalyst-directing o-DPPB group, as exemplified by highly position-, regio-, and diastereoselective hydroformylation of the geranyl and neryl o-DPPB esters. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.

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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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Various hydrogenases and formate-dependent hydrogen production in Citrobacter amalonaticus Y19

An isolate Citrobacter amalonaticus Y19 showed a typical mixed-acid fermentation with lactate and acetate as major end products when grown anaerobically on glucose and pyruvate, respectively. Production of hydrogen (H2) from glucose, formate, and reduced methylviologen (MV) and benzylviologen (BV) by the resting cells of Y19 indicates the presence of formate hydrogen lyase (FHL) activity and other hydrogenases. Study with subcellular fractions of Y19 exhibited that the FHL activity, dependent on soluble formate dehydrogenase activity, was detected in the broken cell extract, but not in the soluble or particulate fraction which are separated by centrifugation at 35, 000 ¡Á g. Hydrogen production in the presence of reduced MV or BV was observed in both the soluble and particulate fractions. Uptake hydrogenase activity was observed in both the fractions when the oxidized forms of MV and BV were supplied as electron acceptor. In the soluble fraction, when formate was coupled with oxidized form of MV or BV, hydrogen production activity was recovered. These results indicate that, similar to E. coli, the strain Y19 expresses two different hydrogenases, one as the FHL complex and another as membrane-associated enzyme.

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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