Bromo

Distribution by Scientific Domains
Distribution within Chemistry

Terms modified by Bromo

  • bromo derivative

  • Selected Abstracts


    Oxidative Addition of B,Br Bonds to Pd0: Synthesis and Structure of trans -Bromo(boryl)palladium Complexes

    EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 9 2008
    Holger Braunschweig
    Abstract The oxidative addition of several bromoboranes to the Pd0 species [Pd(PCy3)2] yielded the novel palladium boryl complexes trans -[(Cy3P)2Pd(Br)(BCat)] (1) (Cat = 1,2-dioxophenylene), trans -[(Cy3P)2Pd(Br)(BCat,)] (2) (Cat, = Cat-4- tBu) and trans -[(Cy3P)2Pd(Br){B(X)X,}] {X = Br, X, = NMe2 (3), Pip (4) (Pip = NC5H10), Mes (5) [Mes = 2,4,6-(CH3)3C6H2]}. Compounds 1,5 were characterized by multinuclear NMR spectroscopy in solution; single crystals for X-ray analyses were acquired from 2 and 3, which thus allowed comparison of the structural data. The few palladium boryl complexes published so far were obtained by ,-bond metathesis; the oxidative addition of the corresponding bromoboranes to Pd0 has not yet been reported.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source]


    Polymeric, Molecular, and Cation/Anion Arrangements in Chloro-, Bromo-, and Iododiruthenium(II,III) Carboxylate Compounds

    EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 12 2003
    M. Carmen Barral
    Abstract The synthesis and characterization of the anhydrous compounds [Ru2X(,-O2CR)4] [R = CH2CH2OPh, X = Cl (1a), Br (2a), I (3a); R = CMePh2, X = Br (5a), I (6a)] and of the solvated complexes [Ru2X(,-O2CR)4(H2O)] [R = CH2CH2OPh, X = Cl (1b), I (3b); R = CMePh2, X = Cl (4b), Br (5b), I (6b)] are described. Thermogravimetric analyses have been used to confirm the anhydrous or solvated natures of the complexes. The crystal structures of 1b·2MeOH, 3b·0.5H2O, and 4b have been investigated by X-ray diffraction and none of them shows the usual polymeric arrangement reported for tetracarboxylatodiruthenium(II,III) compounds. The structure of 3b·0.5H2O consists of cationic and anionic units, [Ru2(,-O2CCH2CH2OPh)4(H2O)2][Ru2I2(,-O2CCH2CH2OPh)4], and represents the first reported crystal structure of a tetracarboxylato(iodo)diruthenium(II,III) derivative. The structures 1b·2MeOH and 4b each show the presence of discrete dinuclear molecules. The crystal structure of [Ru2Cl(,-O2CCMePh2)4(H2O)] demonstrates that diruthenium compounds with the same halide and carboxylate ligands may adopt polymeric or discrete molecular dispositions. Magnetic susceptibility measurements of the complexes in the 2,300 K range have been carried out. Complex 2a shows a strong antiferromagnetic coupling, consistent with the existence of linear chains in the solid state. The complexes [Ru2X(,-O2CR)4(H2O)] show weak through-space antiferromagnetic coupling, in accordance with non-polymeric structures. The magnetic behaviour of 1a, 3a, 5a, and 6a suggests a mixture of arrangements. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source]


    A Radical Version of the Bromo- and the Iodocyclization of Bis(homoallylic) Alcohols , The Synthesis of Halogenated Tetrahydrofurans by Stereoselective Alkoxyl Radical Ring Closures

    EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 20 2003
    Jens Hartung
    Abstract A new synthesis of bromo- and iodomethyl-substituted tetrahydrofurans has been devised. The sequence starts with the conversion of aryl-functionalized bis(homoallylic) alcohols 1 into N -alkenoxythiazole-2(3H)-thiones 6 or pyridine-2(1H)-thiones 7. When photolyzed in the presence of appropriate trapping reagents, thiones 6 and 7 efficiently liberated substituted 4-penten-1-oxyl radicals 2, which underwent synthetically useful 5- exo -trig cyclizations. Cyclized radicals 3 were trapped with BrCCl3 or an adequate iodine atom donor (either n -C4F9I or diethyl 2-iodo-2-methyl malonate) to provide halocyclization products 4 or 5. This strategy has been applied for the synthesis of 3-, 4-, or 5-phenyl-substituted 2-(1-bromo-1-methylethyl)tetrahydrofurans 4a,c (75,90%, 36,96% de), which were not attainable as major products from polar, for example NBS-mediated, bromocyclizations. Aryl-substituted 2-iodomethyl tetrahydrofurans 5 (46,80%) were prepared in a similar way starting from N -alkenoxypyridine-2(1H)-thiones 7 and a suitable iodine atom donor. Diastereomerically pure iodides cis - 5 and trans - 5 served as starting materials for a stereochemical analysis of disubstituted tetrahydrofurans by NMR spectroscopy and X-ray diffraction analysis. The results of this investigation clarified that all new alkoxyl radical cyclizations followed in terms of regio- and diastereoselectivity the general guidelines which had been established for this type of ring-closure reaction. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source]


    A Rapid and Efficient Stereoselective Synthesis of (Z)- and (E)-Allyl Bromides from Baylis,Hillman Adducts Using Bromo(dimethyl)sulfonium Bromide,

    HELVETICA CHIMICA ACTA, Issue 7 2006
    Biswanath Das
    Abstract Treatment of Baylis,Hillman adducts 1 with bromo(dimethyl)sulfonium bromide, Br(Me2)S+Br,, in MeCN was found to stereoselectively afford (Z)- and (E)-allyl bromides 2. The reaction is rapid at room temperature, high-yielding, and highly stereoselective. [source]


    Catalytic Asymmetric Bromoamination of Chalcones: Highly Efficient Synthesis of Chiral ,-Bromo-,-Amino Ketone Derivatives,

    ANGEWANDTE CHEMIE, Issue 35 2010
    Yunfei Cai
    Sparsam mit dem Katalysator: In der unter milden Bedingungen über eine Bromonium-Zwischenstufe verlaufenden Titelreaktion wurden mit 0.05,Mol-% eines C2 -symmetrischen N,N,-Dioxid-Scandium(III)-Komplexes hervorragende Resultate erzielt (siehe Schema). [source]


    ChemInform Abstract: InX3 -Catalyzed Haloamidation of Vinyl Arenes: A Facile Synthesis of ,-Bromo- and ,-Fluoroamides.

    CHEMINFORM, Issue 25 2009
    J. S. Yadav
    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 of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source]


    ChemInform Abstract: Palladium-Catalyzed ,-Arylation of Aldehydes with Bromo- and Chloroarenes Catalyzed by [{Pd(allyl)Cl}2] and dppf or Q-phos.

    CHEMINFORM, Issue 29 2008
    Giang D. Vo
    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 of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source]


    Polyaniline-Supported Palladium-Catalyzed Suzuki,Miyaura, Cross-Coupling of Bromo- and Chloroarenes in Water.

    CHEMINFORM, Issue 46 2007
    M. Lakshmi Kantam
    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]


    A Stereoselective Synthesis of Vinyl Bromides from ,-Bromo-,,,-Unsaturated Ketones Involving Fragmentation of ,,,-Unsaturated Sulfinic Acids.

    CHEMINFORM, Issue 31 2006
    A New Approach to the Vitamin D Rings CD Building Blocks.
    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]


    A Radical Version of the Bromo- and the Iodocyclization of Bis(homoallylic) Alcohols , The Synthesis of Halogenated Tetrahydrofurans by Stereoselective Alkoxyl Radical Ring Closures.

    CHEMINFORM, Issue 7 2004
    Jens Hartung
    No abstract is available for this article. [source]


    ChemInform Abstract: Highly Stereoselective Radical Reduction of ,-Bromo-,-fluoro-,-hydroxy Esters with Tributyltin Hydride Leading to threo-,Fluoro-,-hydroxy Esters.

    CHEMINFORM, Issue 27 2002
    Kazuhide Mima
    Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source]


    ChemInform Abstract: Stereoselective Synthesis of Thiochroman-4-ones by Ring Transformation of Chiral 5-Ylidene-1,3-dioxan-4-ones with 2-Bromothiophenol via Bromo,Lithium Exchange.

    CHEMINFORM, Issue 11 2002
    Akbar Ali
    Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source]


    ChemInform Abstract: A One-Pot Synthesis of (E)-,-Bromo-,,,-unsaturated Esters and Their Trifluoromethylation: A General and Stereoselective Route to (E)-,-Trifluoromethyl-.alpha±beta.-unsaturated Esters.

    CHEMINFORM, Issue 48 2001
    Feng-Ling Qing
    Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source]


    Synthesis and Electronic Properties of Monodisperse Oligophenothiazines

    CHEMISTRY - A EUROPEAN JOURNAL, Issue 8 2008
    Markus Sailer Dr.
    Abstract Starting from N -hexylphenothiazine, a versatile construction kit of brominated and borylated phenothiazines can be easily prepared by a sequence of bromination, bromo,lithium exchange/borylation, and Suzuki coupling. Subsequent Suzuki arylation of the building blocks gives soluble, monodisperse, and structurally well defined oligophenothiazines in good yields. The molecular weights at the peak maximum (Mp), obtained by GPC (gel permeation chromatography), and the actual molecular weights of the oligomer series, obtained by mass spectrometry, show excellent correlation. A QM/MM conformational analysis for the complete series reveals that the obvious butterfly-shaped phenothiazine structure multiplies and significantly reduces the hydrodynamic volume of the oligomers. The electronic properties (absorption and emission spectroscopy and cyclic voltammetry) give reasonable correlations with the chain length. With regard to the emission maxima, the effective conjugation length is already reached with the hexamer. Oligophenothiazines are highly fluorescent, with high fluorescence quantum yields, and are simultaneously highly electroactive, with low oxidation potentials. Ausgehend von N -Hexylphenothiazin kann leicht ein vielseitiger Baukasten aus bromierten und borylierten Phenothiazinen über eine Sequenz aus Bromierung, Bromo,Lithium-Austausch/Borylierung und Suzuki Kupplung hergestellt werden. Die nachfolgende Suzuki-Arylierung der Bausteine führt in guten Ausbeuten zu löslichen, monodispersen und strukturtreuen Oligophenothiazinen. Die Molekulargewichte beim Peakmaximum (Mp), die aus GPC (Gelpermeationschromatographie) erhalten werden und die tatsächlichen Molekulargewichte der Oligomeren, erhalten durch Massenspektrometrie, ergeben eine exzellente Korrelation. Die QM/MM-Konformationsanalyse der gesamten Serie zeigt, das der Effekt der Schmetterlingsstruktur der Phenothiazine sich vervielfältigt und so das hydrodynamische Volumen der Oligomere deutlich verkleinert. Die elektronischen Eigenschaften der Oligomere (Absorptions- und Emissionsspektroskopie und Cyclovoltammetrie) korrelieren mit der Kettenlänge. Im Falle der Emissionsmaxima wird die effektive Konjugationslänge bereits mit dem Hexamer erreicht. Oligophenothiazine fluoreszieren mit hohen Fluoreszenzquantenausbeuten und erweisen sich gleichzeitig wegen ihrer niedrigen Oxidationspotenziale als äußerst elektroaktiv. [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 2006
    Lukas 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]


    Low doses of bromo- and iododeoxyuridine produce near-saturation labeling of adult proliferative populations in the dentate gyrus

    EUROPEAN JOURNAL OF NEUROSCIENCE, Issue 3 2005
    Kevin A. Burns
    Abstract Cell proliferation can be detected by the incorporation of tritiated thymidine (3H-dT) or halopyrimidines during DNA synthesis in progenitor cells. Administration of two thymidine analogues at different times can further determine the cell-cycle kinetics of proliferating cells. Traditionally, this was done by combining bromodeoxyuridine (BrdU) immunocytochemistry and 3H-dT autoradiography, or by BrdU and iododeoxyuridine (IdU) double-labeling using two mouse antibodies. However, these methods either require lengthy exposure time or involve complicated histological procedures for differentiating between two antibodies of the same species. Here we report a simple and reliable method of distinguishing BrdU- and IdU-labeled cells by immunofluorescence. This method uses a mouse monoclonal antibody that recognizes both BrdU and IdU and a rat anti-BrdU antibody that has no cross-reactivity with IdU. When combined with species-specific secondary antibodies that are conjugated to different fluorophores, this method identifies BrdU- and IdU-incorporation as doubly and singly labeled cells, respectively. This method has broad applications. First, we demonstrate that this method can distinguish mouse cortical neurons generated on different embryonic days. Second, by administering IdU and BrdU at varying intervals, we used this method to calculate that the length of S-phase of neural progenitor cells in the adult mouse dentate gyrus is approximately 6 h. Finally, we show that a six-fold higher concentration of IdU detects only 10% more cells than the standard dose of BrdU (50 mg/kg) using the double-labeling method. These results suggest that the standard dose of BrdU is sufficient to label the majority of proliferative populations in the S-phase in pulse labeling experiments. [source]


    Vinylic Halogenation in 4-Alkylidenazetidin-2-ones

    EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 15 2007
    Gianfranco Cainelli
    Abstract The synthesis of a new family of halogenated ,-lactams by oxidative substitution of vinylic hydrogen in conjugated double bonds of 4-alkylidenazetidinones is reported. Optimised procedures give good to excellent yields of chloro, bromo, iodo and nitro derivatives. A mechanism to explain the direct vinylic substitution is proposed. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source]


    A Radical Version of the Bromo- and the Iodocyclization of Bis(homoallylic) Alcohols , The Synthesis of Halogenated Tetrahydrofurans by Stereoselective Alkoxyl Radical Ring Closures

    EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 20 2003
    Jens Hartung
    Abstract A new synthesis of bromo- and iodomethyl-substituted tetrahydrofurans has been devised. The sequence starts with the conversion of aryl-functionalized bis(homoallylic) alcohols 1 into N -alkenoxythiazole-2(3H)-thiones 6 or pyridine-2(1H)-thiones 7. When photolyzed in the presence of appropriate trapping reagents, thiones 6 and 7 efficiently liberated substituted 4-penten-1-oxyl radicals 2, which underwent synthetically useful 5- exo -trig cyclizations. Cyclized radicals 3 were trapped with BrCCl3 or an adequate iodine atom donor (either n -C4F9I or diethyl 2-iodo-2-methyl malonate) to provide halocyclization products 4 or 5. This strategy has been applied for the synthesis of 3-, 4-, or 5-phenyl-substituted 2-(1-bromo-1-methylethyl)tetrahydrofurans 4a,c (75,90%, 36,96% de), which were not attainable as major products from polar, for example NBS-mediated, bromocyclizations. Aryl-substituted 2-iodomethyl tetrahydrofurans 5 (46,80%) were prepared in a similar way starting from N -alkenoxypyridine-2(1H)-thiones 7 and a suitable iodine atom donor. Diastereomerically pure iodides cis - 5 and trans - 5 served as starting materials for a stereochemical analysis of disubstituted tetrahydrofurans by NMR spectroscopy and X-ray diffraction analysis. The results of this investigation clarified that all new alkoxyl radical cyclizations followed in terms of regio- and diastereoselectivity the general guidelines which had been established for this type of ring-closure reaction. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source]


    A Rapid and Efficient Stereoselective Synthesis of (Z)- and (E)-Allyl Bromides from Baylis,Hillman Adducts Using Bromo(dimethyl)sulfonium Bromide,

    HELVETICA CHIMICA ACTA, Issue 7 2006
    Biswanath Das
    Abstract Treatment of Baylis,Hillman adducts 1 with bromo(dimethyl)sulfonium bromide, Br(Me2)S+Br,, in MeCN was found to stereoselectively afford (Z)- and (E)-allyl bromides 2. The reaction is rapid at room temperature, high-yielding, and highly stereoselective. [source]


    Kinetics and simulations of reaction between safranine- O and acidic bromate and role of bromide therein

    INTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 9 2002
    S. B. Jonnalagadda
    Safranine- O, a dye of the phenazinium class, was found to exhibit intricate kinetics during its reaction with bromate at low pH conditions. Under conditions of excess concentrations of acid and bromate, safranine- O (SA+) initially depleted very slowly (k = (3.9 ± 0.3) × 10,4 M,3 s,1) but after an induction time, the reaction occurred swiftly. Bromide exhibited a dual role in the reaction mechanism, both as an autocatalyst and as an inhibitor. The added bromide increased the initial rate of depletion of SA+, but delayed the transition to rapid reaction. The overall stiochiometric reaction was found to be 6SA+ + 4 BrO3, = 6SP + 3N2O + 3H2O + 6H+ + 4Br,, where SP is 3-amino-7-oxo-2,8-dimethyl-5-phenylphenazine. The fast kinetics of the reaction between aqueous bromine and safranine- O (k = (2.2 ± 0.1) × 103 M,1 s,1) are also reported in this paper A 17-step mechanism, consistent with the overall reaction dynamics and supported by simulations, is proposed and the role of various bromo and oxybromo species is also discussed. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 542,549, 2002 [source]


    Iron-Catalyzed Oxidative Mono- and Bis-Phosphonation of N,N -Dialkylanilines

    ADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 10 2010
    Wei Han
    Abstract The dehydrogenative ,-phosphonation of substituted N,N -dialkylanilines by dialkyl H -phosphonates was achieved under mild conditions by using environmentally benign iron(II) chloride as catalyst and tert -butyl hydroperoxide as oxidant. The reaction proceeded in the presence of electron-donating (methoxy, methyl, benzyl) and electron-withdrawing ring-substitutents (bromo, carbonyl, carboxyl, m -nitro) in moderate to good yields. The X-ray crystal structure of N -(5,5-dimethyl-2-oxo-2,5 -[1,3,2]dioxaphosphinan-2-yl-methyl)- N -methyl- p -toluidine was determined. Bis-(4-(dimethylamino)phenyl)methane and bis-4,4,-(dimethylamino)benzophenone underwent bisphosphonation selectively by respective monophosphonation at the remote dimethylamino groups. Furthermore, the use of excess dialkyl H -phosphonate and oxidant allowed us to functionalize both methyl groups of N(CH3)2 in N,N -dimethyl- p -toluidine and N,N -dimethylaminomesidine, respectively, to obtain ,,,,-bisphosphonatoamines in high yield. [source]


    Arylethyne Bromoboration,Negishi Coupling Route to E - or Z -Aryl-Substituted Trisubstituted Alkenes of ,98% Isomeric Purity.

    ADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 4 2010
    New Horizon in the Highly Selective Synthesis of Trisubstituted Alkenes
    Abstract The hitherto unprecedented palladium-catalyzed cross-coupling of (Z)-,-bromo-,-arylethenylboranes can be made to proceed satisfactorily through (1) the use of highly catalytically active bis(tri- tert -butylphosphine)palladium or dichloro[N,N -bis-(2,6-diisopropylphenyl)imidazol-2-yl](m -chloropyridine)palladium and (2) conversion of the dibromoboryl group to the (pinacol)boryl group. Thus, a wide variety of carbon groups can be used to substitute bromine in ,98% stereo- and regioselectivity, while suppressing the otherwise dominant ,-debromoboration. Together with the alkylethyne-based protocols, the alkyne bromoboration,Negishi coupling tandem process has emerged as the most widely applicable and highly selective route to trisubstituted alkenes including those that are otherwise difficult to access. [source]


    Preparation of Arylphosphonates by Palladium(0)-Catalyzed Cross-Coupling in the Presence of Acetate Additives: Synthetic and Mechanistic Studies

    ADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 18 2009
    Marcin 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]


    A Practical Transition Metal-Free Aryl-Aryl Coupling Method: Arynes as Key Intermediates

    ADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 17-18 2007
    Frédéric
    Abstract Upon treatment of various aryllithium intermediates with 1,2-dibromobenzene or 1-bromo-2-iodobenzene, dissymmetrical ortho,ortho, -di-, tri- and even tetrasubstituted bromo- or iodobiaryls become readily available. The crucial steps in all these reactions were the nucleophilic addition of the organolithium precursor to a transient aryne species released from it by ,-elimination of a lithium halide and, stabilization of the resulting 2-biaryllithium intermediate by in situ transfer of bromine or iodine from the starting material. This straightforward transition metal-free access to biaryls allows the preparation of highly valuable halobiaryls on a gram scale in excellent yields. These precursors can be subsequently functionalized by highly regioselective halogen/metal permutations into a vast variety of target molecules. This was demonstrated in the synthesis of several mono- and diphosphine ligands. [source]


    Nanocrystalline Magnesium Oxide-Stabilized Palladium(0): An Efficient and Reusable Catalyst for Suzuki and Stille Cross-Coupling of Aryl Halides

    ADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 15 2005
    Kantam, M. Lakshmi
    Abstract A nanocrystalline magnesium oxide-stabilized palladium(0) catalyst is prepared by counterion stabilization of PdCl42, with nanocrystalline MgO followed by reduction. This ligand-free heterogeneous nanocrystalline MgO-stabilized nanopalladium [NAPMgPd(0)] catalyst using the basic MgO in place of basic ligands exhibits excellent activity in Suzuki and Stille cross-coupling of haloarenes (chloro, bromo and iodo) to afford the unsymmetrical biaryls. The catalyst is quantitatively recovered by simple filtration and reused for four cycles with almost consistent activity. [source]


    Bichalcophenes: A concise synthesis of formyl ester- and cyano ester-substituted bithiophenes, bifurans, and furanothiophenes

    JOURNAL OF HETEROCYCLIC CHEMISTRY, Issue 1 2010
    Abdelbasset A. Farahat
    Syntheses of new formyl ester- and cyano ester-substituted bithiophenes, bifurans, and furanothiophenes in good yield are described. The key synthetic step uses Stille coupling of appropriately substituted bromo 5-ring heterocycles with stannyl-substituted 5-ring heterocycles. J. Heterocyclic Chem., (2010). [source]


    Radiosynthesis of novel 18F-labelled derivatives of indiplon as potential GABAA receptor imaging tracers for PET

    JOURNAL OF LABELLED COMPOUNDS AND RADIOPHARMACEUTICALS, Issue 3 2008
    Steffen Fischer
    Abstract The involvement of gamma amino butyric acid (GABA) receptors in a variety of neurological and psychiatric diseases has promoted the development and use of radiolabelled benzodiazepines (BZ) for brain imaging by PET. However, these radioligands are unable to distinguish between the various subtypes of GABAA receptors. Novel non-BZ such as the pyrazolo-pyrimidine indiplon proved to be selective for the ,1 -subunit of the GABAA receptor. Here, we describe the syntheses of four novel 18F-labelled indiplon derivatives. Radiosyntheses were performed via n.c.a. 18F-nucleophilic substitution starting from the tosyl, bromo, and 4-nitrobenzoyl precursors to obtain fluorine substituted N -alkylamide side chain derivatives of indiplon, followed by multistep purification using semi-preparative high-performance liquid chromatography and solid phase extraction. Tosyl and bromo precursors were converted into 18F-labelled indiplon derivatives with good and reproducible radiochemical yield (RCY) (35,70%, decay corrected), high radiochemical purity (,98.5%), and high specific activity (,>,150,GBq/µmol). By contrast, a low RCY (5,10%) and specific activity (10,15,GBq/µmol) were achieved for the 4-nitrobenzoyl precursor. Copyright © 2008 John Wiley & Sons, Ltd. [source]


    Synthesis of carbon-14 labelled (5Z)-4-bromo-5-(bromomethylene)-2(5H)-furanone: a potent quorum sensing inhibitor

    JOURNAL OF LABELLED COMPOUNDS AND RADIOPHARMACEUTICALS, Issue 10 2004
    Tobias Persson
    Abstract The potent quorum sensing inhibitor (5Z)-4-bromo-5-(bromomethylene)-2(5H)-[2- 14C]furanone has been prepared in five steps in 7.7% overall yield starting from bromo[1- 14C]acetic acid. Condensation of ethyl bromo[1- 14C]acetate with ethyl acetoacetate followed by decarboxylation was accelerated by microwave heating to afford [1- 14C]levulinic acid. Subsequently, bromination and oxidation gave the targeted furan-2-one with a radiochemical purity of > 97% and a specific activity of 57 mCi/mmol. Copyright © 2004 John Wiley & Sons, Ltd. [source]


    Substitution-reduction: an alternative process for the [18F]N -(2-fluoroethylation) of anilines

    JOURNAL OF LABELLED COMPOUNDS AND RADIOPHARMACEUTICALS, Issue 4 2004
    Emmanuelle Briard
    Abstract Substitution of a halo atom (chloro or bromo) in easily prepared N -haloacetyl-anilines with no-carrier added (NCA) cyclotron-produced [18F]fluoride ion (18F, t1/2= 109.8 min; ,+=96.9%), followed by reduction with borane,tetrahydrofuran (BH3,THF), provides an alternative route to NCA [18F]N -(2-fluoroethyl)-anilines. This two-step and one-pot process is rapid (,50 min) and moderately high yielding (,40% decay-corrected radiochemical yield (RCY) overall). In the nucleophilic substitution reaction, 18-crown-6 is preferred to Kryptofix® 222 as complexing agent for the solubilization of the counter-ion (K+), derived from an added metal salt, in acetonitrile. Weakly basic potassium bicarbonate is preferred as the added metal salt. Inclusion of a small amount of water, equating to 4,5 molar equivalents relative to 18-crown-6, base or precursor (held in equimolar ratio), is beneficial in preventing the adsorption of radioactivity onto the wall of the glass reaction vessel and for achieving high RCY in the nucleophilic substitution reaction. BH3,THF is effective for the rapid reduction of the generated [18F]N -fluoroacetyl-aniline to the [18F]N -(2-fluoroethyl)-aniline. Copyright © 2004 John Wiley & Sons, Ltd. [source]


    A new practical tritium labelling procedure using sodium borotritide and tetrakis(triphenylphosphine)palladium(0)

    JOURNAL OF LABELLED COMPOUNDS AND RADIOPHARMACEUTICALS, Issue 14 2001
    Tohru Nagasaki
    Abstract A simple, mild and versatile new tritium (3H) labelling method on a micro scale using sodium borotritide (NaB3H4) and a transition,metal complex catalyst is described. 3H-labelled compounds were prepared effectively by 3H hydrogenolysis of appendant functional groups in target compounds. The appendant functional group such as bromo, iodo or sulfonate in various target compounds can be replaced by tritium (3H) in moderate yields. The new method was established by optimization of the reaction conditions and examination of its applicability using four types of model substrates in tracer runs. Then, various drug candidates and ligands for drug discovery were labelled with tritium on a micro scale. The specific radioactivity of the 3H-labelled compounds used for the studies on receptor binding ranged from 12 to 20 Ci/mmol. Copyright © 2001 John Wiley & Sons, Ltd. [source]