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Palladium
Kinds of Palladium Terms modified by Palladium Selected AbstractsOne-Step Reduction of Chalcones to Saturated Alcohols by Ammonium Formate/Palladium on Carbon: A Versatile Method.CHEMINFORM, Issue 39 2006Carlos Kleber Z. Andrade Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF. [source] PALLADIUM, PLATINUM: Road to Recovery?AFRICA RESEARCH BULLETIN: ECONOMIC, FINANCIAL AND TECHNICAL SERIES, Issue 12 2010Article first published online: 9 FEB 2010 No abstract is available for this article. [source] Redox Active Two-Component Films of Palladium and Covalently Linked Zinc Porphyrin,Fullerene DyadELECTROANALYSIS, Issue 9 2006Marta Plonska Abstract Redox active films have been generated electrochemically by the reduction of dyads consisting of fullerene C60 covalently linked to zinc meso -tetraphenyloporphyrin, ZnPC60, and palladium acetate. The films are believed to consist of a polymeric network formed via covalent bonds between the palladium atoms and the fullerene moieties. In these films, the zinc porphyrin moiety is covalently linked to the polymeric chains through the pyrrolidine ring of the fullerene. The ZnPC60/Pt films are electrochemically active in both positive and negative potential excursions. At positive potentials, two oxidation steps for the zinc porphyrin are observed. In the negative potential range, electron transfer processes involving the zinc porphyrin and the fullerene entities are observed. Film formation is also accompanied by palladium deposition on the electrode surface. The presence of a metallic phase in the film influences its morphology, structure and electrochemical properties. [source] Mono-, Bi-, Tri- and Tetranuclear Palladium(II), Copper(I), and Gold(I) Complexes of Morpholine- and N -Methylpiperazine-Functionalized Cyclodiphosph(III)azans, cis -[(tBuN-,)2(PNC4H8X)2] (X = O, NMe)EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 26 2010Maravanji S. Balakrishna Abstract Bis(amido)cyclodiphosphazanes, cis -[(tBuN-,)2(PNC4H8O)2] (2) and cis -[(tBuN-,)2(PNC4H8NMe)2] (3) were synthesized by treating the corresponding amines with cis -[ClP(tBuN-,)2PCl] (1). The stoichiometric reactions of 2 or 3 with elemental sulfur and selenium afforded the bis-chalcogenides, cis -[(tBuN-,)2(P(E)NC4H8X)2] (X = O, E = S; 4, X = NMe, E = S; 5, X = O, E = Se; 6, X = O, E = Se; 7). The reactions of 2 or 3 with [PdCl2(SMe2)2] produced exclusively the mononuclear trans -[PdCl2{(tBuN-,)2(PNC4H8X)2}2] (X = O; 8, X = NMe; 9), whereas the reactions with [Pd(,-Cl)(,3 -C3H5)]2 afforded the bimetallic complexes [{PdCl(,3 -C3H5)}2{(tBuN-,)2(PNC4H8X)2}] (X = O; 10, X = NMe; 11) in good yield. Treatment of 2 or 3 with [AuCl(SMe2)] in 1:1 and 1:2 molar ratios yielded the mono- and binuclear complexes, [{AuCl(tBuN-,)2(PNC4H8O)2}] (X = O; 12, X = NMe; 13), [{AuCl}2{(tBuN-,)2(PNC4H8O)2}] (X = O; 14, X = NMe; 15), respectively. The PdII (8) and AuI (12) complexes were used as metallo-ligands to prepare homo- and heterometallic complexes, trans -[PdCl2{(tBuN-,)2(PNC4H8O)2}2{Pd(,3 -C3H5)Cl}2] (16), trans -[PdCl2{(tBuN-,)2(PNC4H8O)2}2(AuCl)2] (17), and [Cu(CH3CN)(,-Cl)2Cu(CH3CN){(tBuN-,)2(PNC4H8O)2}2(AuI)2](18). The crystal structures of 2, 4, 7,9, 14, 15, and 18 were established by single-crystal X-ray diffraction studies. [source] Palladium(II) Phosphotungstate Derivatives: Synthesis and Characterization of the [Pdx{WO(H2O)}3,x{A,,-PW9O34}2](6+2x), AnionsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 4 2009Richard Villanneau Abstract A series of PdII derivatives of the [P2W21O71(H2O)3]6, heteropolytungstate with the general formula [Pdx{WO(H2O)}3,x{A,,-PW9O34}2](6+2x), (x = 1,3) is described. These compounds are obtained by the reaction between [PdII(NO3)2]·H2O and the corresponding vacant polyoxometalates in water. They are characterized by IR and multinuclear NMR (31P and 183W) spectroscopy. Compound K10[Pd2{WO(H2O)}{A,,-PW9O34}2]·30H2O was characterized by XRD: it crystallized in the orthorhombic space group Pcmn with parameters a = 18.119(3) Å, b = 19.729(3) Å, c = 24.856(5) Å, V = 8886(3) Å3.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Interactions of Cationic Palladium(II)- and Platinum(II)-,3 -Allyl Complexes with Fluoride: Is Asymmetric Allylic Fluorination a Viable Reaction?EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 7 2006Lukas Hintermann Abstract The complex cations [M(,3 -R2All)(PPFPz{3- tBu})]+ (M = PdII, R2All = 1,3-diphenylallyl, 1,3-dicyclohexylallyl, indenyl; M = PtII, R2All = 1,3-diphenylallyl; PPFPz-{3- tBu} = 3- tert -butyl-1-{1-[2-diphenylphosphanyl-ferrocenyl]ethyl}-1H -pyrazole)have been prepared as salts with PF6, or SbF6,. They have been characterized by NMR spectroscopy in solution and by X-ray crystallography in the solid state. Their reactions with sources of nucleophilic and "naked" fluoride have been investigated by multinuclear NMR spectroscopy. The PdII complexes did not undergo any nucleophilic substitution with concomitant release of allyl fluorides. The dicyclohexylallyl fragment was released as a 1,3-diene by elimination, but with other allyl complexes nonspecific decomposition reactions predominated. The complex [Pt(,3 -1,3-Ph2C3H3)(PPFPz{3- tBu})]PF6 underwent an anion exchange with Me4NF to give [Pt(1,3-Ph2C3H3)(PPFPz{3- tBu})]F which existed as a mixture of interconverting allyl isomers in solution at ambient temperature. For the bromide salt, [Pt(,3 -1,3-Ph2C3H3)(PPFPz{3- tBu})]Br, allyl isomerization was slow at ambient temperature. Precursors of Pt0 reacted with bromo-1,3-diphenylprop-2-ene to give [Pt2(,-Br)2(,3 -1,3-Ph2All)2] and precursors of Pd0 underwent oxidative additions with bromo- and fluoro-1,3-diphenyl-2-propene to give 1,3-diphenylallyl complexes of PdII. Therefore, the nucleophilic attack of fluoride on the allyl fragment of PdII complexes is endergonic, and the high energy barrier of this step is difficult to overcome in a catalytic allylic fluorination reaction. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] Synthesis and Structural Characterisation of Palladium and Group-12 Metal Complexes with a Hybrid Phosphanylphosphonate Ferrocene LigandEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 5 2006Abstract Diethyl [1,-(diphenylphosphanyl)ferrocenyl]phosphonate (1) was synthesised by stepwise metallation/functionalisation of 1,1,-dibromoferrocene and studied as a ligand for palladium(II) and group-12 metals. Treatment of [PdCl2(cod)] (cod = ,2:,2 -cycloocta-1,5-diene) with 1 in 1:1 or 1:2 molar ratios gave, respectively, the dinuclear, chloride-bridged complex [{Pd(,-Cl)Cl(1 -,P2)}2] (2) and the mononuclear complex trans -[PdCl2(1 -,P2)2] (3), where 1 coordinates exclusively through the phosphane function. The reactions between 1 and group-12 metal bromides MBr2 in a 1:1 molar ratio gave the adducts [MBr2(1)] [M = Zn (4), Cd (5), and Hg (6)], whose crystal structures change considerably with the metal ion. Thus, whereas 4 is a molecular complex with 1 coordinating as an O1,P2 -chelate, its cadmium(II) analogue is a polymer built up from symmetric {CdBr(,-Br)}2 units interconnected by pairs of O1,P2 -bridging phosphanylphosphonate ligands. Finally, the mercury(II) complex 6 is a halide-bridged dimer, [{Hg(,-Br)Br(1 -,P2)}2]. However, this compound is structurally fluxional in solution (NMR spectra) and, in the crystal, it attains a structure similar to 5 owing to weak interactions between mercury and phosphonate-O1 atoms from adjacent molecules. An isomer to 6, [{HgBr2(1 -,2O1,P2)}2] (7), was isolated from attempted alkylation of 6 and structurally characterised as a dimer, where ligands 1 bridge two {HgBr2} units. All compounds were studied by spectroscopic methods (IR, NMR, mass) and the solid-state structures of 1, 2·,H2O, 3·4,CHCl3, 4, 5, 6·5,C6H6, and 7 have been determined by single-crystal X-ray diffraction. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] Synthesis and Characterization of Heterotrinuclear Complexes of Nickel and Palladium with Pyridinecarboxylate as Bridging LigandsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 15 2005José Ruiz Abstract Heterotrinuclear pyridinecarboxylate complexes of nickel(II) and palladium(II) of the types [Ni(mcN3)(pyridinecarboxylate)]2{,-[Pd(C6F5)2]}(PF6)2 [mcN3 = 2,4,4-trimethyl-1,5,9-triazacyclododec-1-ene (Me3 -mcN3) or 2,4,4,9-tetramethyl-1,5,9-triazacyclododec-1-ene (Me4 -mcN3)] have been prepared by two different routes. The corresponding monomeric pyridinecarboxylate complexes of nickel and the monomeric pyridinecarboxylic acid/ester complexes of palladium have also been prepared. The crystal structures of two precursors [Ni(Me4 -mcN3)(NC5H4 -3-COO)]PF6 and cis -[Pd(C6F5)2(NC5H4 -4-CH2COOCH3)2] have been established by X-ray diffraction. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] Regioselective Metal-Catalyzed Hydrophosphinylation of Alkynes: Synthesis of Enantiopure ,- or ,-Substituted Vinylphosphane OxidesEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 26 2009Amélie Duraud Abstract Palladium was found to catalyze regioselective Markovnikov addition of chiral enantiopure 1r -oxo-2c,5t -diphenylphospholane (1) to terminal alkynes, whereas rhodium catalysis offers selectively the (E)-anti-Markovnikov adduct. This strategy offers rapid access to chiral and enantiopure ,- or ,-substituted-1-alkenylphospholanes. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Alkyne Hydroarylations with Chelating Dicarbene Palladium(II) Complex Catalysts: Improved and Unexpected Reactivity Patterns Disclosed Upon Additive Screening,EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 19 2009Andrea Biffis Abstract Palladium(II) complexes with a ligand set made from a chelating N-heterocyclic dicarbene ligand and two weakly coordinating anions (generally introduced in situ upon addition of 2 equiv. of a suitable silver salt) were found to be very active and selective catalysts for the room-temperature hydroarylation of alkynes at low catalyst loading (0.1 mol-%). Moreover, the screening of various strong acids as reaction promoters revealed that both the strength of the acid and the coordinating ability of its conjugated base influence the catalytic performance. Most remarkably, the use of HBF4 together with a dicarbene Pd complex catalyst provides a dramatic change in the selectivity of the reaction, with the prevalent formation of a product stemming from the insertion of two molecules of alkyne into the aromatic C,H bond. The results presented herein highlight the fact that the dicarbene ligand, apart from stabilising the catalyst, is also able to enhance catalytic activity and, most notably, to steer the reaction selectivity towards novel products. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Palladium(II) Chloride and a (Dipyridin-2-ylmethyl)amine-Derived Palladium(II) Chloride Complex as Highly Efficient Catalysts for the Synthesis of Alkynes in Water or in NMP and of Diynes in the Absence of ReoxidantEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 19 2005Juan Gil-Moltó Abstract The (dipyridin-2-ylmethyl)amine-derived palladium chloride complex 1 and PdCl2 are efficient catalysts for cross-coupling reactions between terminal alkynes and aryl iodides or bromides under modified Sonogashira,Cassar,Heck conditions. The alkynylation can be performed under copper-free conditions in water at reflux or at room temperature under air with pyrrolidine as base and tetra- n -butylammonium bromide (TBAB) as additive, with TONs of up to 7,×,104 and TOFs(h,1) of up to 6666. Terminal alkynes can be arylated in NMP as well under copper- and amine-free conditions at 110 °C or room temperature, with tetra- n -butylammonium acetate (TBAA) acting as base with TONs up to 2,×,105 and TOFs (h,1) up to 66,666. In general, complex 1 displays a slightly higher efficiency than PdCl2 as catalyst and maintains the same activity after five consecutive runs. Alternatively, these alkynylation processes can be carried out under microwave heating conditions. The homocoupling of terminal alkynes to the corresponding 1,3-diynes proceeds under phosphane-free conditions with the (dipyridin-2-ylmethyl)amine-derived palladium chloride complex 1 or with PdCl2 as catalysts and with CuI as cocatalyst in NMP with use of either TBAA or pyrrolidine as bases. This Glaser-type reaction can be performed at 110 °C or at room temp. in the presence of air without the use of a reoxidant. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] Total Synthesis of Murrayanine Involving 4,5-Dimethyleneoxazolidin-2-ones and a Palladium(0)-Catalyzed Diaryl InsertionHELVETICA CHIMICA ACTA, Issue 8 2007Pablo Bernal Abstract A new total synthesis of the natural carbazole murrayanine (1) was developed by using the 4,5-dimethyleneoxazolidin-2-one 12 as starting material. The latter underwent a highly regioselective Diels,Alder cycloaddition with acrylaldehyde (=prop-2-enal; 13) to give adduct 14 (Scheme,3). Conversion of this adduct into diarylamine derivative 9 was carried out via hydrolysis and methylation (Scheme,4). Differing from our previous synthesis, in which such a diarylamine derivative was transformed into 1 by a PdII -stoichiometric cyclization, this new approach comprised an improved cyclization through a more efficient Pd0 -catalyzed intramolecular diaryl coupling which was applied to 9, thus obtaining the natural carbazole 1 in a higher overall yield. [source] Insertion Reactions of 1,2-Disubstituted Olefins with an , -Diimine Palladium(II) ComplexHELVETICA CHIMICA ACTA, Issue 8 2006Carla Carfagna Abstract The migratory insertions of cis or trans olefins CH(X)CH(Me) (X,=,Ph, Br, or Et) into the metal,acyl bond of the complex [Pd(Me)(CO)(iPr2dab)]+ [B{3,5-(CF3)2C6H3}4], (1) (iPr2dab,=,1,4-diisopropyl-1,4-diazabuta-1,3-diene,=,N,N, -(ethane-1,2-diylidene)bis[1-methylethanamine]) are described (Scheme,1). The resulting five-membered palladacycles were characterized by NMR spectroscopy and X-ray analysis. Experimental data reveal some important aspects concerning the regio- and stereochemistry of the insertion process. In particular, the presence of a Ph or Br substituent at the alkene leads to the formation of highly regiospecific products. Moreover, in all cases, the geometry of the substituents in the formed palladacycle was the same as in the starting olefin, as a consequence of a cis addition of the Pd,acyl fragment to the CC bond. Reaction with CO and MeOH of the five-membered complex derived from trans-, -methylstyrene (=,[(1E)-prop-1-enyl]benzene) insertion, yielded the 2,3-substituted , -keto ester 9 with an (2RS,3SR)-configuration (Scheme,3). [source] Palladium on Carbon-Catalyzed Synthesis of Benzil Derivatives from 1,2-Diarylalkynes with DMSO and Molecular Oxygen as Dual OxidantsADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 10 2010Shigeki Mori Abstract A palladium on carbon (Pd/C)-catalyzed synthetic method for the preparation of benzil derivatives from 1,2-diarylalkynes has been established using dimethyl sulfoxide (DMSO) and molecular oxygen as dual oxidants. Regardless of the electrical nature of the functional groups on the aromatic rings, 1,2-diarylalkynes were oxidized to the corresponding benzil derivatives in high to excellent yields. Furthermore, the oxidation could efficiently be catalyzed by both the dry and wet types of Pd/C under atmospheric conditions. [source] Extremely Efficient Cross-Coupling of Benzylic Halides with Aryltitanium Tris(isopropoxide) Catalyzed by Low Loadings of a Simple Palladium(II) Acetate/Tris(p -tolyl)phosphine SystemADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 10 2010Chi-Ren Chen Abstract Highly efficient coupling reactions of benzylic bromides or chlorides with aryltitanium tris(isopropoxide) [ArTi(O- i- Pr)3] catalyzed by a simple palladium(II) acetate/tris(p -tolyl)phosphine [Pd(OAc)2/ P(p -tolyl)3] system are reported. The coupling reactions proceed in general at room temperature employing low catalyst loadings of 0.02 to 0.2,mol%, affording coupling products in excellent yields of up to 99%. For benzylic bromides bearing strong electron-withdrawing cyano (CN) or trifluoromethyl (CF3) substituents, the reactions require a higher catalyst loading of 1,mol%, or the reactions are carried out at 60,°C. The catalytic system also tolerates (1-bromoethyl)benzene bearing ,-hydrogen atoms while using a catalyst loading of 1,mol% to afford the coupling product in a 70% yield. [source] Examination of the Aromatic Amination Catalyzed by Palladium on CharcoalADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 9 2010Anna Komáromi Abstract The Buchwald,Hartwig amination of aryl halides with secondary amines and functionalized aromatic amines catalyzed by solid-supported palladium is reported. The choices of ligand, base and solvent are crucial for the successful coupling. The amination of aromatic iodides, bromides and chlorides can be easily achieved with palladium on charcoal in the presence of a biphenylphosphane-type ligand at 80,110,°C. In addition, the palladium on charcoal catalyst is easily separable after the reaction, and reusable several times with only small activity loss. [source] Palladium(II) Complexes of C2 -Bridged Chiral Diphosphines: Application to Enantioselective Carbonyl-Ene ReactionsADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 8 2010He-Kuan Luo Abstract (11bR,11,bR)-4,4,-(1,2-Phenylene)bis[4,5-dihydro-3H -dinaphtho[2,1- c:1,,2,- e]phosphepin] [abbreviated as (R)-BINAPHANE], (3R,3,R,4S,4,S,11bS,11,bS)-4,4,-bis(1,1-dimethylethyl)-4,4,,5,5,-tetrahydro-3,3,-bi-3H -dinaphtho[2,1- c:1,,2,- e]phosphepin [(S)-BINAPINE], (1S,1,S,2R,2,R)-1,1,-bis(1,1-dimethylethyl)-2,2,-biphospholane [(S,S,R,R)-TANGPHOS] and (2R,2,R,5R,5,R)-1,1,-(1,2-phenylene)bis[2,5-bis(1-methylethyl)phospholane] [(R,R) -i- Pr-DUPHOS] are C2 -bridged chiral diphosphines that form stable complexes with palladium(II) and platinum(II) containing a five-membered chelate ring. The Pd(II)-BINAPHANE catalyst displayed good to excellent enantioselectivities with ee values as high as 99.0% albeit in low yields for the carbonyl-ene reaction between phenylglyoxal and alkenes. Its Pt(II) counterpart afforded improved yields while retaining satisfactory enantioselectivity. For the carbonyl-ene reaction between ethyl trifluoropyruvate and alkenes, the Pd(II)-BINAPHANE catalyst afforded both good yields and extremely high enantioselectivities with ees as high as 99.6%. A comparative study on the Pd(II) catalysts of the four C2 -bridged chiral diphosphines revealed that Pd(II)-BINAPHANE afforded the best enantioselectivity. The ee values derived from Pd(II)-BINAPHANE are much higher than those derived from the other three Pd(II) catalysts. A comparison of the catalyst structures shows that the Pd(II)-BINAPHANE catalyst is the only one that has two bulky (R)-binaphthyl groups close to the reaction site. Hence it creates a deep chiral space that can efficiently control the reaction behavior in the carbonyl-ene reactions resulting in excellent enantioselectivity. [source] Ligand-Free and Heterogeneous Palladium on Carbon-Catalyzed Hetero-Suzuki,Miyaura Cross-CouplingADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 4 2010Yoshiaki Kitamura Abstract A ligand-free and heterogeneous palladium on carbon (Pd/C)-catalyzed hetero-Suzuki,Miyaura coupling reaction has been developed. The protocol enables the construction of both heterocyclic-alicyclic and heterocyclic-heterocyclic biaryl derivatives in good to excellent yields. Furthermore, Pd/C could be reused. The time-course study clarified that palladium was leached into the reaction media as the reaction proceeded and then completely deposited on the carbon support. [source] Aerobic Oxidation of Primary Aliphatic Alcohols to Aldehydes Catalyzed by a Palladium(II) Polyoxometalate CatalystADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 2-3 2010Delina Barats Abstract A hexadecyltrimethylammonium salt of a "sandwich" type polyoxometalate has been used as a ligand to attach a palladium(II) center. This Pd-POM compound was an active catalyst for the fast aerobic oxidation of alcohols. The unique property of this catalyst is its significant preference for the oxidation of primary versus secondary aliphatic alcohols. Since no kinetic isotope effect was observed for the dehydrogenation step, this may be the result of the intrinsically higher probability for oxidation of primary alcohols attenuated by steric factors as borne out by the higher reactivity of 1-octanol versus 2-ethyl-1-hexanol. The reaction is highly selective to aldehyde with little formation of carboxylic acid; autooxidation is inhibited. No base is required to activate the alcohol. The fast reactions appear to be related to the electron-acceptor nature of the polyoxometalate ligand that may also facilitate alcohol dehydrogenation in the absence of base. [source] Palladium(II)-Phosphine Complexes Supported on Magnetic Nanoparticles: Filtration-Free, Recyclable Catalysts for Suzuki,Miyaura Cross-Coupling ReactionsADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 2-3 2010Sankaranarayanapillai Shylesh Abstract An organic-inorganic hybrid heterogeneous nanocatalyst system was synthesized by covalent grafting a palladium dichloride complex of the type (L)2PdCl2 (L=trimethoxysilyl-functionalized triphenylphosphine) on silica-coated magnetic nanoparticles. It is a highly active and recyclable catalyst for the Suzuki,Miyaura cross-coupling reaction. The new catalyst can easily be separated from the reaction mixture by applying an external magnetic field and can be recycled many times without any loss of activity. [source] The First General and Selective Palladium(II)-Catalyzed Alkoxycarbonylation of Arylboronates: Interplay among Benzoquinone-Ligated Palladium(0) Complex, Organoboron, and Alcohol SolventADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 2-3 2010Yoshihiko Yamamoto Abstract Methoxycarbonylation of aryl- and alkenylboron compounds was performed using the palladium(II) acetate/triphenylphosphine [Pd(OAc)2/PPh3] catalyst with p -benzoquinone as a stoichiometric oxidant in methanol at ambient temperature to obtain the corresponding methyl esters in good yields. A wide variety of functional groups including various carbonyl functionalities, nitrile, nitro, sulfone, and unprotected pyrrole rings were tolerated in the methoxycarbonlation, while the use of higher alcohols except for tert -butanol afforded various p -chlorobenzoates in moderate to high yields. The catalytic alkoxycarbonylation proceeded without any acid or base additive, and an oxidative transmetalation step is proposed to explain the exceptional efficacy of this protocol. DFT and MP2 calculations support the proposed mechanism. [source] Microwave-Assisted Synthesis of N-Heterocyclic Carbene- Palladium(II) ComplexesADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 1 2010Abstract The microwave-assisted synthesis of two different types of N-heterocyclic carbene-palladium(II) complexes, (NHC)Pd(acac)Cl (NHC=N-heterocyclic carbene; acac=acetylacetonate) and (NHC)PdCl2(3-chloropyridine), has been carried out. A drastic reduction in reaction times (20 to 88 times faster, depending on the complex) was observed when compared to the previously described, conventionally-heated synthesis of these complexes. The protocol also allowed for the synthesis of (IPr)Pd(acac)Cl [IPr=1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene] on a 5-mmol scale in 30,min, with the reactants loaded in air. [source] Preparation of Arylphosphonates by Palladium(0)-Catalyzed Cross-Coupling in the Presence of Acetate Additives: Synthetic and Mechanistic StudiesADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 18 2009Marcin Kalek Abstract An efficient protocol for the synthesis of arylphosphonate diesters via a palladium-catalyzed cross-coupling of H-phosphonate diesters with aryl electrophiles, promoted by acetate ions, was developed. A significant shortening of the cross-coupling time in the presence of the added acetate ions was achieved for bidentate and monodentate supporting ligands, and for different aryl electrophiles (iodo, bromo and triflate derivatives). The reaction conditions were optimized in terms of amount of the catalyst, supporting ligands, and source of the acetate ion used. Various arylphosphonates, including those of potential biological significance, were synthesized using this newly developed protocol. Some mechanistic aspects of the investigated reactions are also discussed. [source] Catalytic 1,2-Dicyanation of Alkynes by Palladium(II) under Aerobic ConditionsADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 11-12 2009Shigeru Arai Abstract A stereoselective 1,2-dicyanation of various alkynes in the presence of trimethylsilyl cyanide (TMSCN) by palladium(II) catalysis under aerobic conditions is investigated. This reaction includes two cyanation pathways, syn - and anti -cyanopalladation to alkynes that are activated by Pd(II). High syn -selectivity was observed in the reaction using terminal alkynes that have bulky substituents at a propargyl position and aliphatic internal alkynes. Furthermore, a dramatic acceleration was observed with substrates having an N -arenesulfonyl functionality at a propargyl position, this indicates that both sulfoxide and carbon-carbon triple bond act as Lewis bases to Pd(II). [source] Regioselective Palladium(0)-Catalyzed Cross-Coupling Reactions and Metal-Halide Exchange Reactions of Tetrabromothiophene: Optimization, Scope and LimitationsADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 10 2009ng Thanh Tùng Abstract The Suzuki reaction of tetrabromothiophene with arylboronic acids provides a regioselective approach to various 5-aryl-2,3,4-tribromothiophenes, symmetrical 2,5-diaryl-3,4-dibromothiophenes, and tetraarylthiophenes. Unsymmetrical 2,5-diaryl-3,4-dibromothiophenes are prepared by Suzuki reaction of 5-aryl-2,3,4-tribromothiophenes. Tetraarylthiophenes containing two different types of aryl groups are obtained by Suzuki reactions of 2,5-diaryl-3,4-dibromothiophenes. During the optimization of the conditions of each individual reaction, the solvent, the catalyst and the temperature play an important role. In several cases, classical conditions [use of tetrakis(triphenylphosphane)palladium(0), Pd(PPh3)4, as the catalyst] gave excellent yields. The yields of those transformations which failed or proceeded sluggishly could be significantly improved by application of a new biarylmonophosphine ligand developed by Buchwald and co-workers. Regioselective metal-halide exchange reactions of tetrabromothiophene provide a convenient approach to various 2,5-disubstituted 3,4-dibromothiophenes. 5-Alkyl-2-trimethylsilyl-3,4-dibromothiophenes could be prepared in one pot by sequential addition of trimethylchlorosilane and alkyl bromides. The reaction of tetrabromothiophene with methyl chloroformate and subsequent Suzuki reactions afforded 3,4-diaryl-2,5-bis(methoxycarbonyl)thiophenes. [source] A Mild, One-Pot Synthesis of Arylamines via Palladium- Catalyzed Addition of Aryl Aldehydes with Amines and Arylboronic Acids in WaterADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 5 2009Ajuan Yu Abstract A mild, one-pot synthesis of diarylmethylamines via the palladium-catalyzed addition of aryl aldehydes with amines and arylboronic acids is reported. Best results were obtained in neat water with ammonium chloride as additive, affording diarylmethylamine derivatives as the main products. [source] Palladium(II)-Catalyzed Domino Reaction of 2-(1-Alkynyl)-2-alken-1-ones with Nucleophiles: Scope, Mechanism and Synthetic Application in the Synthesis of 3,4-Fused Bicyclic Tetrasubstituted FuransADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 4 2009Yuanjing Xiao Abstract Described herein is the development of a palladium(II)-catalyzed two- or three-component reaction of 2-(1-alkynyl)-2-alken-1-ones with nucleophiles and allylic chlorides. Various types of nucleophiles such as O- , N- , C -based nucleophiles and olefin-tethered O- , N- , C -based nucleophiles were investigated. The scope, mechanism and application of this Pd(II)-catalyzed domino reaction were studied. In these transformations, the palladium catalyst exhibits a dual role, serving simultaneously as a Lewis acid and a transition metal. Two possible reaction pathways (cross-coupling reaction vs. Heck reaction) from the same intermediate furanylpalladium species were observed. The reaction pathway is dependent on the property of the nucleophile and the length of the tethered chain as well. When olefin-tethered O -based nucleophiles were used, only the cross-coupling reaction pathway was observed, in contrast, both reaction pathways were observed when olefin-tethered C -based nucleophiles were employed. The product ratio is dependent on the length of the tethered chain. Furthermore, ring-closing metathesis (RCM) of corresponding furans with CC bonds provides an easy method for the preparation of functionalized oxygen-heterocycles , 3,4-fused bicyclic furans. It is also noteworthy that allylic chloride can be as an oxidant besides its well known function as an alkylating reagent. [source] Improved Suzuki,Miyaura Reactions of Aryldiazonium Salts with Boronic Acids by Tuning Palladium on Charcoal Catalyst PropertiesADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 4 2009François-Xavier Felpin Abstract An improved Suzuki,Miyaura cross-coupling reaction of aryldiazonium tetrafluoroborates with boronic acids catalyzed by a highly active palladium catalyst supported on charcoal is described as an extremely practical and efficient protocol. A properties-activity study of various catalysts clearly established that the optimal catalytic activity was obtained with palladium nanoparticles having a low oxidation degree and uniformly dispersed on the charcoal. The optimized reaction conditions allow the cross-coupling to proceed at room temperature without any base and ligand in technical grade methanol. Although the catalyst could not be recycled, the low palladium contamination of the solvent and product after a simple filtration of the palladium on charcoal (Pd/C) renders the present protocol competitive and safer for the environment compared to more conventional homogeneous conditions. We have highlighted the efficiency of this novel protocol by a short synthesis of the fungicide Boscalid®. [source] One-Pot Synthesis of Highly Substituted Allenylidene Derivatives via Palladium- or Nickel-Catalyzed Tandem Michael Addition,Cyclization ReactionADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 1-2 2009Yun Shi Abstract A simple and tandem synthetic approach, which offers an efficient, direct route to highly substituted indenes, has been developed by palladium- or nickel-catalyzed cyclization of propargylic compounds and nitrogen nucleophiles. The reaction takes place under mild conditions, and a possible mechansim is proposed. [source] Efficient and Practical Cross-Coupling of Arenediazonium Tetrafluoroborate Salts with Boronic Acids Catalyzed by Palladium(0)/Barium CarbonateADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 6 2008François-Xavier Felpin Abstract The cross-coupling reaction of arenediazonium tetrafluoroborate salts with boronic acids catalyzed by the unusual palladium(0)/barium carbonate catalyst is described as an extremely practical and highly efficient alternative to classical homogeneous conditions. Reactions are conducted under mild conditions at room temperature without any base and ligand. The opportunity of preparing unsymmetrical terphenyls in a one-pot process is also demonstrated. Finally, the power of this methodology is highlighted by the synthesis of Bifenazate. [source] | |||||||||||||||||||||||||||||||