- A Palladium-Free Sonogashira Coupling Protocol Employing an in Situ Prepared Copper/Chelating 1,2,3-Triazolylidene System
-
A new, palladium-free Sonogashira coupling reaction protocol using a catalytic system that comprises a simple, cheap, widely available copper salt and a chelating 1,2,3-triazolylidene ligand precursor is reported. This protocol provides the desired coupling products in moderate to very good yields.
- Tonis, Efstathios,Stein, Felix,Stamatopoulos, Ioannis K.,Stubbe, Jessica,Zarkadoulas, Athanasios,Sarkar, Biprajit,Vougioukalakis, Georgios C.
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supporting information
p. 616 - 620
(2020/11/25)
-
- Electrocatalytic property, anticancer activity, and density functional theory calculation of [NiCl(P^N^P)]Cl.EtOH
-
This study describes the electrocatalytic, anticancer, and density functional theory (DFT) studies of a nickel complex, [NiCl(P^N^P)]Cl.EtOH, based on a neutral P^N^P-type pincer ligand (P^N^P = bis[(2-diphenylphosphino)ethyl]amine). The ligand was synthesized without time-consuming and costly amine protection. It was characterized by 1H NMR, 31P NMR, Fourier transform infrared (FT-IR), UV–vis, and single-crystal X-ray diffraction. The complex was isolated as a solvated chloride salt and characterized by FT-IR, UV–visible, 1H NMR, 13C NMR, and 31P NMR spectroscopies as well as single-crystal X-ray diffraction and CHN analysis. The ligand and complex crystallized in a monoclinic P21/c space group. The molecular structure of the complex contains a four-coordinated distorted nickel ion with square-planar geometry. The electrocatalytic hydrogen ion reduction was studied for the nickel complex in an acidic non-aqueous medium. Cyclic voltammetry studies showed that this complex is an efficient electrocatalyst for hydrogen evolution at the potential of the Ni(II/I) couple. As a potential anticancer agent, the biological activities of the Ni complex were tested against two human cancer cell lines (MCF7 and HT29). The IC50 results demonstrated that the nickel complex has better cytotoxic activity than cis-platin against the human breast cancer cell (MCF7) line. DFT calculations were performed to study the kinetics and thermodynamics of the pincer ligand's synthetic procedure and its Ni complex. Time-dependent DFT calculations were performed to calculate the pincer ligand's UV–vis spectra and the complex, which was in agreement with the experimental data. To assign the calculated UV spectra, molecular orbital calculations were performed. Finally, a modified mechanism was proposed for the electrocatalytic hydrogen ion reduction by [Ni(P^N^P)Cl]Cl.EtOH. The theoretical calculations showed that the cycle is thermodynamically favorable.
- Mohammadnezhad, Gholamhossein,Abad, Saeed,Farrokhpour, Hossein,G?rls, Helmar,Plass, Winfried
-
-
- Atypical and Asymmetric 1,3-P,N Ligands: Synthesis, Coordination and Catalytic Performance of Cycloiminophosphanes
-
Novel seven-membered cyclic imine-based 1,3-P,N ligands were obtained by capturing a Beckmann nitrilium ion intermediate generated in situ from cyclohexanone with benzotriazole, and then displacing it by a secondary phosphane under triflic acid promotion. These “cycloiminophosphanes” possess flexible non-isomerizable tetrahydroazepine rings with a high basicity; this sets them apart from previously reported iminophophanes. The donor strength of the ligands was investigated by using their P-κ1- and P,N-κ2-tungsten(0) carbonyl complexes, by determining the IR frequency of the trans-CO ligands. Complexes with [RhCp*Cl2]2 demonstrated the hemilability of the ligands, giving a dynamic equilibrium of κ1 and κ2 species; treatment with AgOTf gives full conversion to the κ2 complex. The potential for catalysis was shown in the RuII-catalyzed, solvent-free hydration of benzonitrile and the RuII- and IrI-catalyzed transfer hydrogenation of cyclohexanone in isopropanol. Finally, to enable access to asymmetric catalysts, chiral cycloiminophosphanes were prepared from l-menthone, as well as their P,N-κ2-RhIII and a P-κ1-RuII complexes.
- Rong, Mark K.,Holtrop, Flip,Bobylev, Eduard O.,Nieger, Martin,Ehlers, Andreas W.,Slootweg, J. Chris,Lammertsma, Koop
-
supporting information
p. 14007 - 14016
(2021/09/09)
-
- Room-temperature reduction of sulfur hexafluoride with metal phosphides
-
Upon treatment with sulfur hexafluoride, alkali metal diphenyl or dicyclohexyl phosphides are oxidized within seconds to tetraphenyl or tetracyclohexyl diphosphines. When bulky di-tert-butylphosphide is employed, fluorophosphine intermediates are detected. This is the first reported reaction of sulfur hexafluoride with metal phosphides, and a rare example of reactivity of sulfur hexafluoride at ambient temperature. This journal is
- Huchenski, Blake S. N.,Speed, Alexander W. H.
-
supporting information
p. 7128 - 7131
(2021/07/28)
-
- CHIRAL TETRADENTATE LIGAND, METHOD FOR PRODUCING SAME AND TRANSITION METAL COMPLEX OF SAID CHIRAL TETRADENTATE LIGAND
-
The present invention relates to a compound represented by the formula (1A). G represents a group selected from the group consisting of a monovalent group represented by the formula (GP) and a monovalent group represented by the form
- -
-
Paragraph 0110-0111
(2020/12/08)
-
- Ready Approach to Organophosphines from ArCl via Selective Cleavage of C-P Bonds by Sodium
-
The preparation, application, and reaction mechanism of sodium phosphide R2PNa and other alkali metal phosphides R2PM (M = Li and K) have been studied. R2PNa could be prepared, accurately and selectively, via the reactions of SD (sodium finely dispersed in mineral oil) with phosphinites R2POR′ and chlorophosphines R2PCl. R2PNa could also be prepared from triarylphosphines and diarylphosphines via the selective cleavage of C-P bonds. Na was superior to Li and K for these reactions. R2PNa reacted with a variety of ArCl to efficiently produce R2PAr. ArCl is superior to ArBr and ArI since they only gave low yields of the products. In addition, Ph2PNa is superior to Ph2PLi and Ph2PK since Ph2PLi did not produce the coupling product with PhCl, while Ph2PK only gave a low yield of the product. An electron-withdrawing group on the benzene ring of ArCl greatly accelerated the reactions with R2PNa, while an alkyl group reduced the reactivity. Vinyl chloride and alkyl chlorides RCl also reacted efficiently. While t-BuCl did not produce the corresponding product, admantyl halides could give the corresponding phosphine in high yields. A wide range of phosphines were prepared by this method from the corresponding chlorides. Unsymmetric phosphines could also be conveniently generated in one pot starting from Ph3P. Chiral phosphines were also obtained in good yields from the reactions of menthyl chlorides with R2PNa. Possible mechanistic pathways were given for the reductive cleavage of R3P by sodium generating R2PNa and the substitution reactions of R2PNa with ArCl generating R2PAr.
- Ye, Jingjing,Zhang, Jian-Qiu,Saga, Yuta,Onozawa, Shunya,Kobayashi, Shu,Sato, Kazuhiko,Fukaya, Norihisa,Han, Li-Biao
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p. 2682 - 2694
(2020/07/30)
-
- Synthesis, structural and toxicological investigations of quarternary phosphonium salts containing the P-bonded bioisosteric CH2F moiety
-
Tertiary alkyl, aryl or amino phosphines PR3 (R = Me, nBu, C2H4CN, NEt2) and the bis[(2-diphenylphosphino)phenyl]ether (POP) were allowed to react with fluoroiodomethane to produce fluoromethyl phosphonium salts in yields between 60-99%. The compounds were characterized by vibrational and NMR spectroscopy and in most cases also by single crystal X-ray diffraction. Diphenyl(fluoromethyl) phosphine was synthesized as a mixed aryl-alkyl-phosphine and the TEP value (Tolman electronic parameter) was determined in order to explain its low reactivity. The molecular and crystal structures of the new fluoromethyl phosphonium salts [R3PCH2F]I with R = Me, C2H2CN and NEt2 as well as of the salt resulting from the fluoromethylation of POP provided additional information on the structural behavior of the bioisoster CH2F group bonded to phosphorus. Hydrogen bonding in the crystal is compared with that observed in the crystal structure of PPh3CH2FI. The toxicity of the sufficiently water soluble salt [Me3PCH2F]I was investigated and the toxicological effect of the CH2F group was compared to that of the bioisoster CH2OH group in THPS. This journal is
- Dubovnik, Sviatlana,Karaghiosoff, Konstantin,Kornath, Andreas,Reichel, Marco,Roidl, Andreas,Unger, Cornelia
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p. 14306 - 14315
(2020/09/03)
-
- CATALYST COMPOSITION COMPRISING THE COMBINATION OF A MONOPHOPSPHINE, A TETRAPHOSPHINE LIGAND AND A HYDROFORMYLATION PROCESS USING IT
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The present invention relates to catalyst compositions for hydroformylation processes and to hydroformylation processes utilizing certain catalysts. In one aspect, a catalyst composition for a hydroformylation process comprises (a) a transition metal; (b)
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-
Page/Page column 25; 26
(2019/12/25)
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- Ethylene selective oligomerization catalyst systems and method for ethylene oligomerization using the same
-
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
- -
-
Paragraph 0098
(2019/04/25)
-
- TETRADENTATE LIGAND, AND PRODUCTION METHOD THEREFOR, SYNTHETIC INTERMEDIATE THEREOF, AND TRANSITION METAL COMPLEX THEREOF
-
The present invention relates to: a compound as a ligand in a variety of catalytic organic synthetic reactions; a method for producing the compound; a synthetic intermediate of the compound; and a transition metal complex which has the compound as a ligand. The compound includes a compound represented by the following general formula (1A):
- -
-
Paragraph 0133-0134
(2019/05/15)
-
- Synthesis, characterization and catalytic application of some novel PNP-Ni(II) complexes: Regio-selective [2+2+2] cycloaddition reaction of alkyne
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Some novel Ni(II) complexes of PN(H)PPh, PN(Me)PiPr and PN(Me)PtBu ligands have been synthesized and characterized using standard analytical and spectroscopic methods such as 1H NMR, 31P NMR, elemental analysis, ESI-MS, UV-Visible spectroscopy and single-crystal X-ray crystallography. In the presence of silver triflate, complex [PN(H)PPhNiBr]2NiBr4 (5) activated the C?Cl bond of dichloromethane at room temperature and afford complex [PN(H)PPhNiCl]OTf (6). We have also performed alkyne [2+2+2] cycloaddition reaction using Ni(II) complexes and observed high regioselectivity of the products. The observed selectivity is well correlating with the electronic feature of alkynes. The [2+2+2] cycloaddition of electron rich alkynes produced 1,3,5-substituted benzene derivatives as a major product whereas the electron deficient alkynes produced 1,2,4-substituted benzene derivatives as a major product.
- Tamizmani, Masilamani,Sivasankar, Chinnappan
-
-
- Efficient chromium-based catalysts for ethylene tri-/tetramerization switched by silicon-bridged/N,P-based ancillary ligands: A structural, catalytic and DFT study
-
High performance catalysts switched by a series of silicon-bridged/N,P-based ancillary ligands have been explored. The precatalyst supported by L1 possessed a large steric bulk and exhibited a high activity of 16.8 × 106 g (mol Cr)-1 h-1 as well as a total selectivity of 99% toward 1-hexene and 1-octene. The selectivity for 1-hexene was adjustable from 59% to 88%. The catalyst bearing an L2 ligand, facilitated by a smaller steric bulk, displayed an identical activity of 13.0 × 106 g (mol Cr)-1 h-1 and a superior selectivity of 75% towards 1-octene under the appropriate conditions. The DFT calculations elucidated the reason for these excellent and tunable activities and selectivities.
- Zhang, Le,Wei, Wei,Alam, Fakhre,Chen, Yanhui,Jiang, Tao
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p. 5011 - 5018
(2017/11/09)
-
- Triphos derivatives and diphosphines as ligands in the ruthenium-catalysed alcohol amination with NH3
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The ruthenium-triphos and diphosphine-catalysed amination of alcohols with ammonia is reported. Various types of triphos derivatives with electron-donating functional group were synthesized and used as ligands in the Ru-catalysed alcohol amination with NH3. The triphos derivatives are effective for the formation of primary amines. On the other hand, if hemilabile diphosphines as tridentate ligands are used, mixtures of secondary-along with primary amines are obtained. It was found that even simple diphosphines can be used as ligands for the selective formation of the secondary amines. The diphosphine system allows a new entry to the Ru-catalysed formation of secondary amines.
- Nakagawa,Derrah,Schelwies,Rominger,Trapp,Schaub
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p. 6856 - 6865
(2016/05/19)
-
- Controlled Oxidation of an NHC-Stabilized Phosphinoaminosilylene with Dioxygen
-
Reaction of the N-heterocyclic carbene-stabilized phosphinoaminosilylene ArN(SiMe3)Si(IiPr)PPh2 (Ar = 2,6-iPr2C6H3, IiPr = 1,3-diisopropyl-4,5-dimethyl-imidazol-2-ylid
- Cui, Haiyan,Zhang, Jianying,Tao, Yunwen,Cui, Chunming
-
-
- Phosphines with N-heterocyclic boranyl substituents
-
A lithio-diazaborole reacted with diamino-chlorophosphines via metathesis to yield previously unavailable phosphinoboranes bearing amino substituents at both the phosphorus and boron atoms, and with Ph2PCl and Mes*PCl2via chloride tr
- Kaaz,Bender,Foerster,Frey,Nieger,Gudat
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p. 680 - 689
(2014/01/06)
-
- Stereocontrolled construction of the tricyclic framework of tiglianes and daphnanes by an oxidative dearomatization approach
-
An appropriately functionalized [5-7-6] tricyclic framework of tigliane and daphnane diterpenes containing seven contiguous stereocenters has been prepared in 10 steps from very simple building blocks in a modular and stereocontrolled fashion. The key fea
- Tong, Guanghu,Liu, Zhi,Li, Pengfei
-
supporting information
p. 2288 - 2291
(2014/05/06)
-
- Investigation of the reductive cleavage of BINAP and application to the rapid synthesis of phospholes
-
A rapid and easy entry into λ3-phospholes and λ4-phosphole oxides derived from BINAP is reported herein featuring a variety of C and Si substituents and functional groups, as well the investigative work on the mechanistic pathway. DFT calculations using B3LYP functionals have been carried out to rationalize the mechanism. The observed experimental 31P resonance shifts were compared with the calculated shifts of the proposed intermediates after calibration of the shielding tensors. The calculations included the use of polarizable continuum models to take into account solvent effects and were found to be in excellent agreement, providing further evidence for the proposed mechanism.
- Gallop, Chris W.D.,Bobin, Mariusz,Hourani, Petra,Dwyer, Jessica,Roe, S. Mark,Viseux, Eddy M. E.
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p. 6522 - 6528
(2013/07/26)
-
- Synthesis, structure, and characterization of dinuclear copper(I) halide complexes with P^N ligands featuring exciting photoluminescence properties
-
A series of highly luminescent dinuclear copper(I) complexes has been synthesized in good yields using a modular ligand system of easily accessible diphenylphosphinopyridine-type P^N ligands. Characterization of these complexes via X-ray crystallographic studies and elemental analysis revealed a dinuclear complex structure with a butterfly-shaped metal-halide core. The complexes feature emission covering the visible spectrum from blue to red together with high quantum yields up to 96%. Density functional theory calculations show that the HOMO consists mainly of orbitals of both the metal core and the bridging halides, while the LUMO resides dominantly on the heterocyclic part of the P^N ligands. Therefore, modification of the heterocyclic moiety of the bridging ligand allows for systematic tuning of the luminescence wavelength. By increasing the aromatic system of the N-heterocycle or through functionalization of the pyridyl moiety, complexes with emission maxima from 481 to 713 nm are obtained. For a representative compound, it is shown that the ambient-temperature emission can be assigned as a thermally activated delayed fluorescence, featuring an attractively short emission decay time of only 6.5 μs at φPL = 0.8. It is proposed to apply these compounds for singlet harvesting in OLEDs.
- Zink, Daniel M.,B?chle, Michael,Baumann, Thomas,Nieger, Martin,Kühn, Michael,Wang, Cong,Klopper, Wim,Monkowius, Uwe,Hofbeck, Thomas,Yersin, Hartmut,Br?se, Stefan
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p. 2292 - 2305
(2013/04/10)
-
- Synthesis of N,P-, S,P-, P,P- and S,P,S-ligands using reactions of cyclopalladated complexes with KPPh2
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Readily available air- and moisture-stable dimeric chloro-bridged CN-, CS- and CP-cyclopalladated complexes with the (sp2)C-Pd bond react with 4.5 equiv. of KPPh2 in THF to give the corresponding P,N-, P,S- and P,P-bidentate ligands
- Korte, Nicholas J.,Stepanova, Valeria A.,Smoliakova, Irina P.
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p. 356 - 362
(2013/10/01)
-
- Group 14 metal terminal phosphides: Correlating structure with |J MP|
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A series of heavier group 14 element, terminal phosphide complexes, M(BDI)(PR2) (M = Ge, Sn, Pb; BDI = CH{(CH3)CN-2,6-iPr 2C6H3}2; R = Ph, Cy, SiMe 3) have been synthesized. Two
- Tam, Eric C. Y.,Maynard, Nicola A.,Apperley, David C.,Smith, J. David,Coles, Martyn P.,Fulton, J. Robin
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p. 9403 - 9415
(2012/11/07)
-
- Highly Active and Selective Ethylene Oligomerization Catalyst and Method of Preparing Hexene or Octene Using the Same
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This invention relates to a chromium complex compound for selective ethylene oligomerization including a chiral ligand, and to a method of selectively preparing 1-hexene or 1-octene from ethylene using the same.
- -
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Page/Page column 7
(2012/06/01)
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- Alkene hydrogenation catalyzed by nickel hydride complexes of an aliphatic PNP pincer ligand
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To investigate metal-ligand cooperativity as a strategy for promoting nickel-catalyzed alkene hydrogenation, cationic and neutral nickel(II) hydride complexes of the aliphatic pincer ligand PNHPCy {PNHPCy = HN[CH2CH2P(Cy)2]2} have been synthesized and characterized. Cationic hydride complex [(PNHP Cy)Ni(H)]BPh4 (2) catalyzed the hydrogenation of styrene and 1-octene under mild conditions. Only low conversion was observed in the hydrogenation of 3,5-dimethoxybenzaldehyde using 2. The neutral hydride complex (PNPCy)Ni(H) (3) was also found to be an alkene hydrogenation catalyst. Mechanistic experiments suggest that for catalyst 2, the hydrogenation reaction proceeds through a pathway involving initial insertion of the alkene into the Ni-H bond. Contrary to the initial hypothesis, reactivity comparisons with the methyl-substituted hydride complex [(PNMePCy)Ni(H)]BPh 4 {PNMePCy = (CH3)N[CH2CH 2P(Cy)2]2} suggest that metal-ligand cooperativity is not involved in these rare examples of mild and homogeneous nickel hydrogenation catalysis. Copyright
- Vasudevan, Kalyan V.,Scott, Brian L.,Hanson, Susan K.
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p. 4898 - 4906
(2013/01/15)
-
- Ethylene oligomerization catalyst systems having enhanced selectivity
-
Disclosed herein is a catalyst system for selective oligomerization of ethylene, which comprises a P—C—C—P frame-work ligand, which is (R1)(R2)P—(R5)CHCH(R6)—P(R3)(R4), and a chromium-based metal compound. Also disclosed is a method of greatly enhancing the activity and selectivity of oligomerization, such as trimerization or tetramerization, using a ligand having a specific steric arrangement structure.
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Page/Page column 11; 12
(2013/02/27)
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- Construction of rhodium(I) and gold(I) macrocycles by transferring a phosphine-functionalized 4,5-diazafluorenide ligand from its copper(I) N-heterocyclic carbene complex
-
We report the synthesis and characterization of a phosphine-functionalized 4,5-diazafluorene ligand, 9-(2-(diphenylphosphino)ethyl)-4,5-diazafluorene (LpH), and its Cu(IPr) complex (IPr = N,N′-bis(2,6- diisopropylphenyl)imidazol-2-ylidene) [Cu(IPr)Lp] (2a), which exhibits a monomeric structure in solution but dimerizes in the solid state. Compound 2a reacts with Rh(PPh3)3Cl, [Rh(COD)Cl] 2, Au(SMe2)Cl, and Au(IPr)Cl to form the macrocyclic complexes [Rh(PPh3)Lp]2 (2b), [Rh(COD)L p]2 (2c), and [AuLp]2 (2d) and the mononuclear complex [Au(IPr)Lp] (2f), respectively, via ligand transfer. Although 2b-d,f could also be synthesized from the deprotonated ligand Lp- and the corresponding metal starting materials directly, the reactions require longer time and give lower yields. The reaction between LpH and Au(SMe2)Cl gives Au(LpH) 2Cl (2e) exclusively.
- Tan, Runyu,Chiu, Frederick Sin Nang,Hadzovic, Alen,Song, Datong
-
body text
p. 2184 - 2192
(2012/06/01)
-
- Green synthesis of fluorinated biaryl derivatives via thermoregulated ligand/palladium-catalyzed Suzuki reaction
-
Fluorinated compounds have attracted considerable attention in pharmaceuticals, agrochemicals and material science due to their unique physical properties. This paper reports an efficient and environmentally benign protocol for the Suzuki reaction of aryl halides with fluorinated arylboronic acids over a thermoregulated ligand/palladium catalyst using water as sole medium, affording a variety of fluorinated biaryls, including fluorinated liquid crystals, in excellent yields. The catalyst could be recycled four times with high activity. The active catalyst was proved to be a palladium/ligand complex via a mercury-poisoning test.
- Liu, Ning,Liu, Chun,Jin, Zilin
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supporting information; experimental part
p. 2641 - 2647
(2011/07/09)
-
- ETHYLENE TETRAMERIZATION CATALYST SYSTEMS AND METHOD FOR PREPARING 1-OCTENE USING THE SAME
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Disclosed herein is a method of preparing 1-octene at high activity and high selectivity while stably maintaining reaction activity by tetramerizing ethylene using a chromium-based catalyst system comprising a transition metal or a transition metal precursor, a cocatalyst, and a P—C—C—P backbone structure ligand represented by (R1)(R2)P—(R5)CHCH(R6)—P(R3)(R4).
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Page/Page column 4
(2010/06/16)
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- PRODUCTION OF LITHIUM DIPHENYLPHOSPHIDE
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Lithium diphenylphosphide solutions in a solvent, e.g., diethoxymethane (DEM), that are more stable than when tetrahydrofuran (THF) is used as a solvent. Methods of producing them are also disclosed.
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Page/Page column 4-8
(2009/10/09)
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- A facile method for promoting activities of ordered mesoporous silica-anchored Rh-P complex catalysts in 1-octene hydroformylation
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This work deals with the promotion of immobilized Rh catalyst activities in olefin hydroformylation by lengthening the alkyl spacers and choosing an active Rh precursor. The flexibility of long chain alkyls was used to free the motion of the anchored Rh c
- Zhou, Wei,He, Dehua
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experimental part
p. 1146 - 1154
(2010/05/18)
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- Convenient methods for the synthesis of a library of hemilabile phosphines
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A series of novel functionalized phosphines of hemilabile character, R 2P(CH2)nZ, have been prepared from diarylphosphines using several synthetic methodologies. The synthetic methods include the alkylation of lithium diar
- Jimenez, M. Victoria,Perez-Torrente, Jesus J.,Bartolome, M. Isabel,Oro, Luis A.
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experimental part
p. 1916 - 1922
(2009/12/28)
-
- Highly efficient synthesis of (Phosphinodihydrooxazole)- (1,5-cyclooctadiene) Iridium complexes
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A highly efficient one-pot procedure for the synthesis of complexes of the type [Ir(COD)(Phox)]X, where Phox is a (chiral) phosphinooxazoline ligand, X = PF6 or B[(3,5-(CF3)2C6H 3)]4 (BARF), is developed. Former reported syntheses demanded the isolation of pure ligands by column chromatography, but the ligands tend to adsorb irreversibly on silica. Moreover, the chromatography has to be performed with careful exclusion of air. The present method avoids this difficulties. The yields of the syntheses are comparable with those starting from the pure ligands. The method is also suitable for the preparation of complexes of the type [Rh(COD)(Phox)]BARF and [Rh(Phox)2]BARF.
- Semeniuchenko, Volodymyr,Khilya, Volodymyr,Groth, Ulrich
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experimental part
p. 1147 - 1158
(2010/03/02)
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- Palladium catalysed alkyne hydrogenation and oligomerisation: A parahydrogen based NMR investigation
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The role phosphine ligands play in the palladium(ii)-bis-phosphine-hydride cation catalysed hydrogenation of diphenylacetylene is explored through a PHIP (parahydrogen induced polarization) NMR study. The precursors Pd(LL′)(OTf)2 (1a-e) [LL′ = dcpe (PCy2CH 2CH2PCy2), dppe, dppm, dppp, cppe (PCy 2CH2CH2PPh2)] are used. Alkyl palladium intermediates of the type [Pd(LL′)(CHPhCH2Ph)](OTf) (2 and 3) are detected and demonstrated to play an active role in hydrogenation catalysis. Magnetization transfer experiments reveal chemical exchange from the α-H of the alkyl ligand of 2a (LL′ = dcpe) and linkage isomer 2e′ (LL′ = cppe) into trans-stilbene on the NMR timescale. Activation parameters (ΔH≠ and ΔS≠) for this transformation have been determined. These experiments, coupled with GC/MS data, indicate that the catalytic activity is greater in methanol, where it follows the order: dcpe > cppe > dppp > dppe > dppm, than in CD 2Cl2. All five of the phosphine systems described are less active than those based on bcope [where bcope is (C8H 14)PCH2-CH2P(C8H14)] and tbucope [where tbucope is (C8H 14)PC6H4CH2P(tBu) 2]. cis, cis-1,2,3,4-Tetraphenyl-buta-1,3-diene is detected as a minor reaction product with Pd(LL′)(PhCH-CHPh-CPh=CHPh)+ (4) also being shown to play a role in the alkyne dimerisation step.
- Lopez-Serrano, Joaquin,Duckett, Simon B.,Dunne, John P.,Godard, Cyril,Whitwood, Adrian C.
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supporting information; body text
p. 4270 - 4281
(2009/02/03)
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- SOLID FORMS COMPRISING (-) O-DESMETHYLVENLAFAXINE AND USES THEREOF
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Solid forms comprising a compound useful in the treatment, prevention and management of various conditions and diseases are provided herein. In particular, the invention provides solid forms comprising (-)-O-desmethylvenlafaxine, including salts thereof, having utility for the treatment, prevention and management of conditions and disorders including, but not limited to, affective disorders such as depression, bipolar and manic disorders, attention deficit disorder, attention deficit disorder with hyperactivity, Parkinson's disease, epilepsy, cerebral function disorders, obesity and weight gain, incontinence, dementia and related disorders.
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Page/Page column 63-65
(2008/12/08)
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- COMBINATIONS OF ESZOPICLONE AND O-DESMETHYLVENLAFAXINE, AND METHODS OF TREATMENT OF MENOPAUSE AND MOOD, ANXIETY, AND COGNITIVE DISORDERS
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One aspect of the present invention relates to pharmaceutical compositions containing two or more active agents that when taken together can be used to treat, e.g., menopause, mood disorders, anxiety disorders, or cognitive disorders. The first component
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Page/Page column 19
(2008/06/13)
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- 1,4-BIS-DIPHOSPHINES, 1,4-BIS-DIPHOSPHITES AND 1,4-BIS- DIPHOSPHONITES FROM OPTICALLY ACTIVE (Z)-OLEFINES AS CHIRAL LIGANDS
-
Chiral diphosphines, diphosphinites, diphosphites and diphosphonites derived from (Z)-2-butenes suitable to act as chiral ligands, complexes between said diphosphines, diphosphinites, diphosphites and diphosphonites and transition metals, and their utilization as chiral catalysts in stereocontrolled reactions, such as diastereo- and enantioselective reduction reactions, diastereo- and enantioselective hydroformylation reactions, diastereo- and enantioselective hydro cyanation reactions. Process for the preparation of said chiral diphosphines, diphosphinites, diphosphites and diphosphonites and process for the preparation of said complexes and for their utilization in stereocontrolled reactions.
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Page/Page column 18-19; 20
(2008/06/13)
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- BISPHOSPHINE, PROCESS FOR PRODUCING THE SAME, AND USE THEREOF
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Bisphosphines represented by the general formula (I) wherein Ar1 and Ar2 each represents an arylene group which may be substituted; R1 and R2 each represents an alkyl group which may be substituted, or an aryl group which may be substituted, or R1 and R2 may combinedly form a ring together with the phosphorus atom bonded thereto; R3 and R4 each represents hydrogen atom or an alkyl group; and the carbon atoms each having R3 and R4 are bonded in positions ortho to the oxygen atom bonded to Ar1 and Ar2: process for production thereof; Group VIII metal complexes comprising said bisphosphines; and process for producing aldehydes, which comprises, on hydroformylation of ethylenically unsaturated compounds with carbon monoxide and hydrogen, using said Group VIII metal complexes.The hydroformylation of ethylenically unsaturated compounds according to the present invention can produce n-aldehydes at higher reaction rate and industrially more advantageously than with catalysts comprising conventional phosphines, while suppressing side reactions such as hydrogenation and isomerization.
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- Activation of silylphosphines by diethyl azodicarboxylate: Novel silylation of alcohols
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A novel activation mode of silylphosphines and an application of that to silylation of alcohols were described. Silylphosphines were found to be instantly activated by means of DEAD and PPTS to form reactive silyl cation equivalents. By using the activate
- Hayashi, Minoru,Matsuura, Yutaka,Watanabe, Yutaka
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p. 1409 - 1411
(2007/10/03)
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- COMPOUNDS COMPRISING PHOSPHORUS-CONTAINING METAL COMPLEXES
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Compounds comprising phosphorus-containing metal complexes can be used in electroluminescent devices and have an emission maximum closer to the blue region of the visible light spectrum. The complexes can be used within an organic active layer in electron
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- Chiral oxo- and oxy-functionalized diphosphane ligands derived from camphor for rhodium(I)-catalyzed enantioselective hydrogenation
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The synthesis of two series of diastereomeric oxo- and oxysubstituted diphosphanes 7a-9a and 7b-9b, as well as an analogous nonfunctionalized diphosphane 17, was performed starting from (R)-camphor. The new diphosphanes were used as ligands in the enantioselective rhodium(I)-catalyzed hydrogenation of functionalized olefins - α- and β-de hydroamino acids and their esters - in order to elucidate the effect of the oxo- and oxy-functional groups. The enantioselectivities, ranging from 2-90% ee, and the rates were strongly dependent on the type and relative position of the oxo or oxy substituent in the catalyst. Possible explanations for the effects are given. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003.
- Komarov, Igor V.,Monsees, Axel,Spannenberg, Anke,Baumann, Wolfgang,Schmidt, Ute,Fischer, Christine,Boerner, Armin
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p. 138 - 150
(2007/10/03)
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- Preparation of biphosphine ligands for incorporation into catalytic complexes
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This invention relates to processes for making phosphorus compounds R2P—X—PR2, R2P—M, R2P—L and R3P, and the novel cation R2P+(L)—X—P+(L)R2, where R represents an optionally substituted hydrocarbyl group, X represents a bridging group, L represents a leaving group and M represents an alkali metal atom. The invention relates further to a process for making a compound R2P—L from a compound R—H via a new process for making the compound R—Li followed by its reaction with a compound Hal2P—L. The compound R2P—X—PR2is a ligand suitable for making catalysts for copolymerizing carbon monoxide and a olefinically unsaturated compound.
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- New flexible synthesis of pyrazoles with different, functionalized substituents at C3 and C5
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Syntheses of pyrazoles featuring a functionalized side chain attached to carbon 3 and varying alkyl and aryl substituents attached to carbon 5 are presented. Installation of R = methyl, isopropyl, tert-butyl, adamantyl, or phenyl groups at C5 is reported
- Grotjahn, Douglas B.,Van, Sang,Combs, David,Lev, Daniel A.,Schneider, Christian,Rideout, Marc,Meyer, Christoph,Hernandez, Genaro,Mejorado, Lupe
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p. 9200 - 9209
(2007/10/03)
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- Synthesis and characterisation of β-aminophosphine ligands on a solid support
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Synthesis and characterization of β-aminophosphine ligands on a solid support was described. An assessment strategy combining complementary on-resin characterization techniques demonstrated the yield and purity of the support-bound ligands. The combination of the applied synthetic and analytical methods represented an innovative and general approach to the solid-phase synthesis of phosphorus ligands.
- Mansour, Amal,Portnoy, Moshe
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p. 952 - 954
(2007/10/03)
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- Using polarization effects to alter chemical reactivity: A simple host which enhances amine nucleophilicity
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(Matrix Presented) The rational design of a bis(phosphine oxide) host which is capable of binding a benzylic amine is presented. The ability of this host to increase the rate of addition of 4-fluorobenzylamine to N-phenylmaleimide is rationalized in terms of the enhancement of the nucleophilicity of the benzylic amine.
- Ashton, Peter R.,Calcagno, Patrizia,Spencer, Neil,Harris, Kenneth D. M.,Philp, Douglas
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p. 1365 - 1368
(2007/10/03)
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- The cathodic cleavage of the S-P bond. Synthesis and electrochemical behaviour of sulfonamide phosphorus analogues
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P-diphenylarylsulfophosphamides can be obtained by condensation of Ph2PLi on various arylsulfonyl chlorides. These sulfonamide phosphorus analogues exhibit facile cathodic cleavage reaction yielding, after quenching, diphenylphosphinic acid and arylsulfide.
- Pilard, Jean-Francois,Simonet, Jacques
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p. 3735 - 3738
(2007/10/03)
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- Synthesis of cycloalkyldiarylphosphines
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Partially sterically-hindered cycloalkyl chlorides are reacted with lithium diarylphosphides in inert liquid hydrocarbon reaction media to form cycloalkyldiarylphosphines. Aryl lithium is coproduced. The process makes it possible to avoid, or at least substantially eliminate, the interaction with or cleavage of cyclic ether reaction media such as tetrahydrofuran, previously the solvent of choice for conducting this type of reaction. Also during the conduct of the present process the chloro-substituted cycloalkane does not undergo any appreciable reaction with the coproduced aryl lithium as it is formed. Thus improvements both in yield and quality of the cycloalkyldiarylphosphine product are made possible. A comprehensive three-step process for converting triarylphosphine to cycloalkyldiarylphosphine is also described.
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- Synthesis of Methyl 6-Deoxy-6-diphenylphosphino-α-D-glucopyranoside: Temperature-Dependence of the Primary O-Tosyl Cleavage Mode
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Methyl α-D-glucopyranoside is converted to methyl 6-p-toluenesulfonyl-2,3,4-tris-O-trimethylsilyl-α-D-glucopyranoside 2 and then reacted with lithium diphenylphosphide in THF. When the reaction is carried out at room temperature and below, S-O cleavage dominates giving methyl 2,3,4-tris-O-trimethylsilyl-α-D-glucopyranoside 3, whereas at 60°C in THF or at 35°C in diethyl ether, C-O cleavage occurs yielding the title carbohydrate-phosphine 4 in good yield after deprotection.
- Dahlhoff, Wilhelm V.,Radkowski, Karin
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p. 891 - 896
(2007/10/03)
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- Investigation of the Purity of Alkali Metal Diphenylphosphides and Their Reactions with Organic Halides. Evidence for Single Electron Transfer
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For the first time the purity of lithium, sodium, and potassium diphenylphosphide, prepared by various methods, has been evaluated using (31)P NMR spectroscopy.A method was developed to prepare each of the phosphides in a high state of purity.Highly pure potassium diphenylphosphide was then allowed to react with p-iodotoluene in order to determine the effect of purity on the SRN1 nature of this reaction.The results were then compared with literature reports which used less pure KPPh2.The mechanism of reaction of alkyl halides with pure alkali metal diphenylphosphides, using the radical probes 6-halo-5,5-dimethyl-1-hexenes and 1-halo-2,2-dimethylhexanes, was investigated.The results provide the first evidence to support single electron transfer (SET) in the reaction of an alkali metal diphenylphosphide with an alkyl halide.SET was found to be the major reaction pathway in the reaction of hindered alkyl iodides (neopentyl type).On the other hand, SET was found to be a minor pathway in the reaction of the corresponding alkyl bromides and chlorides with PPh2(1-).There was no evidence found for SET in the reactions of unhindered alkyl halides with PPh2(1-) although SET participation cannot be rigorously excluded.
- Ashby, E. C.,Gurumurthy, R.,Ridlehuber, R. W.
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p. 5832 - 5837
(2007/10/02)
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- NOVEL ANIONIC CHALCOGENO LIGANDS. TELLUROPHOSPHINITES R2PTe- AND CHALCOGENOTELLUROPHOSPHINATES R2P(Ch)Te-
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Elemental tellurium reacts with diorganylphosphides R2P- to give tellurophosphinites R2PTe- and with chalcogenophosphinites R2PCh- to give chalcogenotellurophosphinates R2P(Ch)Te- R = C6H11, C6H5; Ch = O,S,Se,T
- Bildstein, Benno,Sladky, Fritz
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p. 341 - 347
(2007/10/02)
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- Di(μ-phosphido)cobalt and Nickel Compounds with Trimethylphosphine Ligands
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Several fortuitous preparations and high yield rational syntheses for 2 (1: M = Co; 2: M = Ni) are described. 1 crystallizes in the space group P (no. 2); a = 975.6(5), b = 943.6(5), c = 904.2(5) pm, α = 63.8(1) deg, β = 79.1(1) deg, γ
- Klein, Hans-Friedrich,Gass, Michael,Zucha, Ulf,Eisenmann, Brigitte
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p. 927 - 932
(2007/10/02)
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- Efficient 1,4-Asymetric Induction Utilizing Electrostatic Interaction between Ligand and Substrate in the Asymmetric Hydrogenation of Didehydrodipeptides
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Electrostatic interaction between the amino group of the achiral 3-dimethylaminopropylidenebismethylenebis(diphenylphosphine) (1) and the carboxy group of the substrate enable an effective 1,4-asymmetric induction in the RhI-catalysed hydrogenation of didehydrodipeptides, to give (S,S)-or (R,R)-products selectively.The selectivity reached up to 94percent diastereoisomeric excess with acetyl didehydrodipeptides and 92percent with benzyloxycarbonyl substrates.
- Yamagishi, Takamichi,Ikeda, Satoru,Yatagai, Masanobu,Yamaguchi, Motowo,Hida, Mitsuhiko
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p. 1787 - 1790
(2007/10/02)
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- Synthesis of Phosphino Alkane Sulfonates and Their Corresponding Sulfonic Acids by Reaction of Alkalimetalphosphides with Sultones
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Alkalimetal salts of dialkyl- and diphenylphosphino alkane sulfonic acids (1-4,6,7) were prepared by reaction of alkalimetalphosphides with sulfones at ambient temperature.The sultonates can be converted into the free sulfonic acids by ion exchange.This m
- Paetzold, Eckhardt,Kinting, Annegret,Oehme, Guenther
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p. 725 - 731
(2007/10/02)
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