- Synthesis of ferrocenylketyl radicals by chromium(II) complexes
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Chromium(II)-imino-diacetate (IDA), -ethylenediaminetetra-acetate (EDTA) and -1,3-propanediamine-N,N′-diacetic-N,N′-dipropionate (PDADP) complexes were used as reagents in H2O-DMF solutions at 5pH7 for the preparation of ferrocenylketyl radic
- Ratkovic, Zoran R.,Somsák, L.ászló,Micskei, K.ároly,Zucchi, Claudia,Pályi, Gyula
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- An anodic method for covalent attachment of molecules to electrodes through an ethynyl linkage
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Electroactive organometallic molecules have been covalently attached to electrode surfaces through an ethynyl linkage. The process takes advantage of ethynyl-based radicals generated by anodic oxidation of a lithio-activated terminal ethynyl group. Electrophores containing redox-active ferrocene, cymantrene, or cobaltocenium moieties have been deposited at the one-to-three monolayer level. Both metal-based and ligand-based chemical reactions have been carried out on the surface-modified systems.
- Sheridan, Matthew V.,Lam, Kevin,Geiger, William E.
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- Kinetics of the synthesis of the S-(1-ferrocenylethyl)thioglycolic acid
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A systematic study of the reactions of a number of α-hydroxylated ferrocene derivatives with thioglycolic acid confirms that the reaction is extremely fast, viz., 15-20 min , as compared with earlier procedures (12 h) .The important kinetic parame
- Scutaru, D.,Tataru, Lucia,Mazilu, I.,Scutaru, Brigitte,Lixandru, Tatiana,Simionescu, Cr.
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- Electrochemical Detection of Saccharides by the Redox Cycle of a Chiral Ferrocenylboronic Acid Derivative: a Novel Method for Sugar Sensing
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A chiral ferrocenylboronic acid 1 bearing an intramolecular tertiary amine binds saccharides at ca. pH 7, the complexation event, which can be conveniently detected by an electrochemical method, shows chiral discrimination for certain linear saccharides.
- Ori, Aiichiro,Shinkai, Seiji
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- Model solid-state reactions for the formation of a peripheral layer of organometallic dendrimers. Solid-state α-ferrocenylethylation of phenols
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With the aim of modifying solid dendrite structures, the solid-state reactions of (S)-(-)-(1-trimethylammonio)ethylferrocene iodide with substituted phenols were studied.
- Khrushcheva,Belousova,Loim,Sokolov
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- Synthesis and structure of biologically active ferrocenylalkyl polyfluoro benzimidazoles
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The title compounds were synthesized in quantitative yields by interacting α-hydroxyalkyl ferrocenes with polyfluoroalkyl benzimidazoles in an aqueous-organic medium in the presence of HBF4. The resulting diastereomers and enantiomers were reso
- Snegur, Lubov' V.,Boev, Victor I.,Nekrasov, Yury S.,Ilyin, Mikhail M.,Davankov, Vadim A.,Starikova, Zoya A.,Yanovsky, Alexander I.,Kolomiets, Alexey F.,Babin, Valery N.
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- Enantiomeric-enriched ferrocenes: Synthesis, chiral resolution, and mathematic evaluation of CD-chiral selector energies with ferrocene-conjugates
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Enantiomeric-enriched ferrocene-modified pyrazoles were synthesized via the reaction of the ferrocene alcohol, (S)-FcCH(OH)CH3 (Fc = ferrocenyl), with various pyrazoles in acidic conditions at room temperature within several minutes. X-ray structural data for racemic (R,S)-1N-(3,5-dimethyl pyrazolyl)ethyl ferrocene (1) and its (S)-enantiomer (S)-1 were determined. A series of racemic pyrazolylalkyl ferrocenes was separated into enantiomers by analytical HPLC on βand γcyclodextrins (CD) chiral stationary phases. The quantum chemical calculations of interaction energies of βCD were carried out for both (R)- and (S)-enantiomers. A high correlation between experimental HPLC data and calculated interaction energies values was obtained.
- Snegur, Lubov V.,Borisov, Yurii A.,Kuzmenko, Yuliya V.,Davankov, Vadim A.,Ilyin, Mikhail M.,Ilyin, Mikhail M.,Arhipov, Dmitry E.,Korlyukov, Alexander A.,Kiselev, Sergey S.,Simenel, Alexander A.
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- Synthesis of bis-ferrocenylpyrazoles via ferrocenylalkylation reaction
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Abstract: Regioselective synthesis of bis-ferrocenylpyrazole derivatives in biphasic aquatic–organic system under catalysis with HBF4 was carried out. The regioselectivity of these reactions depending on the electronic effects of substituents i
- Rodionov, Alexey N.,Gerasimova, Maria D.,Osipova, Elena Yu.,Korlyukov, Alexander A.,Peregudov, Alexander S.,Simenel, Alexander A.
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- Synthesis of 1-(1-ferrocenylethyl)-pyridinium chloride and its hybrid materials with lindquist ype polyoxometalates
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A new ferrocene derivative, 1-(1-ferrocenylethyl)-pyridinium (fep = CpFeCp-CH(CH3)-Py+) chloride, and two charge ransfer salts (CTSs) based on the cationic fep donor and Lindqvist ype polyoxometalate acceptors, [fep]2[Mo6O19] (1) and [fep] 2[W6O19] (2), were synthesized. fepCl was characterized by elemental analysis, IR spectroscopy and 1H NMR and the two CTSs were characterized by elemental analysis, IR spectroscopy, UV-vis diffuse reflectance spectrum, cyclic voltammetry, fluorescence spectrum and single crystal X-ray diffraction. X-ray crystallographic studies of the brownish red CTSs 1 and 2 reveal that they are isostructural and crystallize in the monoclinic space group P21/n. In salts 1-2, fep and polyoxoanions are cocrystallized by Coulombic forces, and there also exist the complex C-H?π and π?π stacking interactions between the adjacent fep cations and C-H?O hydrogen bonds between the adjacent fep cations and polyanions. The UV-vis diffuse reflectance spectra indicate the presence of a broad charge ransfer band between 500 and 850 nm for 1-2, and CT character of 1 and 2 is also confirmed by the Mulliken correlation between the CT transition energies and the reduction potentials of the polyoxometalate acceptors. Two new hybrid materials based on 1-(1-ferrocenylethyl)-pyridinium donor and Lindqvist ype polyoxometalate acceptors were synthesized in high yields and their UV-vis diffuse reflectance spectra indicate the presence of a broad charge ransfer band between 500 and 850 nm.
- Niu, Yujuan,Ren, Xiaoyu,Yin, Bin,Wang, Danjun,Xue, Ganglin,Hu, Huaiming,Fu, Feng,Wang, Jiwu
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- Insight into the Thermal Ring-Opening Polymerization of Phospha[1]ferrocenophanes
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A mixture of cis/trans isomers of phospha[1]ferrocenophanes equipped with one iPr group at the α position to the bridging PhP moiety was prepared. Both isomers (cis-4 and trans-4) were obtained as racemates and could be separated so that their thermal properties were investigated individually. The molecular structure of cis-4 was determined by single-crystal X-ray analysis showing a tilt angle α=26.35(8)°. Interconversion between both isomers occurred in the melt at elevated temperatures and revealed that the trans isomer is thermodynamically more stable. Structural and thermodynamic data was complemented by DFT calculations (B3PW91/6-311+G(d,p) and B3PW91-D3(BJ)/6-311+G(d,p)). Performance of thermal ring-opening polymerization (ROP) of trans-4 at 230 °C gave polymers and cyclic oligomers. Gel permeation chromatography (GPC) of the sulfurized polymer resulted in a molecular weight of 62.5 kDa (Mw) and a polydispersity index of 1.39 (PDI). Mass spectrometric analysis of the oligomers showed the presence of cyclic species from dimers to heptamers. After sulfurization, preparative thin layer chromatography led to the separation of three isomeric dimers. Structural characterization of these dimers by single-crystal X-ray analysis led to the conclusion that the Fe?Cp bond breaks during the thermal ROP process. A mechanism similar to the known mechanism of the photolytic ROP of ferrocenophanes is proposed.
- Khozeimeh Sarbisheh, Elaheh,Esteban Flores, Jose,Zhu, Jianfeng,Müller, Jens
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- Group 6 Metal Carbonyl Complexes Supported by a Bidentate PN Ligand: Syntheses, Characterization, and Catalytic Hydrogenation Activity
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We report on the preparation of a series of phosphorus-nitrogen donor ligand complexes [M(CO)4(PN)], where M = Cr, Mo, W and PN is 2-(diphenylphosphino)ethylamine. The organometallic compounds were readily obtained upon reacting the respective metal hexacarbonyls with equimolar amounts of the pertinent ligand in the presence of tetraethylammonium bromide. The PN-ligated metal carbonyls were fully characterized by standard spectroscopic techniques and X-ray crystallography. The ability of the title compounds to function as homogeneous hydrogenation catalysts was probed in the reduction of acetophenone and benzaldehyde derivatives to yield the corresponding alcohols. The reaction setup was easily assembled by simply combining the components in the autoclave on the bench outside an inert-gas-operated glovebox system.
- Faust, Kirill,Topf, Christoph,Vielhaber, Thomas
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p. 4535 - 4543
(2020/12/23)
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- Synthesis of ferrocenyl-containing silicone rubbers via platinum-catalyzed Si–H self-cross-linking
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Self-cross-linkable ferrocenyl-containing polymethylhydrosiloxanes were synthesized. Karstedt's catalyst and cis-[PtCl2(BnCN)2] were examined as cross-linking catalysts at room temperature for the reaction between Si–H groups of the ferrocenyl-containing polymethylhydrosiloxanes. Cis-[PtCl2(BnCN)2] is an effective catalyst that allows cross-linked ferrocenyl-containing silicones (silicone rubbers) to be obtained with no visible mechanical defects (bubbles or cracks) compared with Karstedt's catalyst. The ferrocene content of the ferrocenyl-containing silicone rubbers was found to be approximately 50?wt.% by energy-dispersive X-ray analysis. Compared with cross-linked non-modified polymethylhydrosiloxanes, the ferrocenyl-containing silicone rubbers exhibited improved tensile properties (the tensile strength increased from 0.47 to 0.75?MPa) and a 1.5–2.5 times lower cross-linking degree. The surface resistivity of the ferrocenyl-containing silicone rubbers (50?wt.% ferrocenyl units) was approximately 7 × 109?Ω/□, which was 10,000 times lower than that of pure polymethylhydrosiloxane. The obtained flexible electroactive ferrocenyl-containing silicone rubbers can potentially be applied as coatings for electronic and electrostatic-sensitive devices, interfaces, and sensors.
- Deriabin, Konstantin V.,Lobanovskaia, Ekaterina K.,Kirichenko, Sergey O.,Barshutina, Marie N.,Musienko, Pavel E.,Islamova, Regina M.
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- RETRACTED ARTICLE: The Manganese(I)-Catalyzed Asymmetric Transfer Hydrogenation of Ketones: Disclosing the Macrocylic Privilege
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The bis(carbonyl) manganese(I) complex [Mn(CO)2(1)]Br (2) with a chiral (NH)2P2 macrocyclic ligand (1) catalyzes the asymmetric transfer hydrogenation of polar double bonds with 2-propanol as the hydrogen source. Ketones (43 substrates) are reduced to alcohols in high yields (up to >99 %) and with excellent enantioselectivities (90–99 % ee). A stereochemical model based on attractive CH–π interactions is proposed.
- Passera, Alessandro,Mezzetti, Antonio
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supporting information
p. 187 - 191
(2019/12/11)
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- 1-D manganese(ii)-terpyridine coordination polymers as precatalysts for hydrofunctionalisation of carbonyl compounds
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Reductive catalysis with earth-abundant metals is currently of increasing importance and shows potential in replacing precious metal catalysis. In this work, we revealed catalytic hydroboration and hydrosilylation of ketones and aldehydes achieved by a structurally defined manganese(ii) coordination polymer (CP) as a precatalyst under mild conditions. The manganese-catalysed methodology can be applied to a range of functionalized aldehydes and ketones with turnover numbers (TON) of up to 990. Preliminary results on the regioselective catalytic hydrofunctionalization of styrenes by the Mn-CP catalyst are also presented.
- Johnson, Jahvon,Li, Sihan,Mo, Zixuan,Neary, Michelle C.,Zeng, Haisu,Zhang, Guoqi,Zheng, Shengping
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supporting information
p. 2610 - 2615
(2020/03/05)
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- Practical and selective hydroboration of aldehydes and ketones in air catalysed by an iron(ii) coordination polymer
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The in air catalytic hydroboration of ketones and aldehydes with pinacolborane by an iron(ii) coordination polymer (CP) is carried out under mild and solvent-free conditions. The precatalyst is highly active towards a wide range of substrates including functionalized ketones and aldehydes in the presence of KOtBu as an activator, achieving a high turnover number (TON) of up to 9500. Excellent chemoselectivity to aldehydes over ketones was also revealed, which is in sharp contrast with the results obtained under inert atmosphere using the same catalyst system. This catalyst observed here is not only highly efficient but also recyclable for reuse for at least 5 times without losing its effectiveness.
- Zhang, Guoqi,Cheng, Jessica,Davis, Kezia,Bonifacio, Mary Grace,Zajaczkowski, Cynthia
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p. 1114 - 1121
(2019/03/12)
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- Process for preparing (S)-1-ferrocene ethyl dimethylamine
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The invention discloses a process for preparing (S)-1-ferrocene ethyl dimethylamine. In the preparation process, acetylferrocene is used as a raw material, and a complex obtained by reacting a metal Ir complex with a chiral ferrocene tridentate ligand L* is used as a catalyst, (S)-1-ferrocenyl ethanol is prepared by asymmetric catalytic hydrogenation, and the(S)-1-ferrocene ethyl dimethylamine isprepared by acetylation and dimethylamine substitution reaction. Compared with a traditional chiral separation method for preparing the (S)-1-ferrocene ethyl dimethylamine, the process has main beneficial effects of mild reaction conditions, simple operation, good stereoselectivity, high yield, short production cycle, small amount of three wastes , easy industrialization, and large implementationvalue and social and economic benefits.
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Paragraph 0050; 0051; 0052
(2018/09/11)
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- Rhodium-Catalyzed Asymmetric Allylation of Malononitriles as Masked Acyl Cyanide with Allenes: Efficient Access to β,γ-Unsaturated Carbonyls
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A rhodium-catalyzed regio- and enantioselective intermolecular allylation of malononitriles as masked acyl cyanides (MAC) with terminal and symmetrical internal allenes is reported. A RhI/Josiphos catalytic system combined with subsequent oxidative degradation of the primary adducts enables a straightforward access to α-branched, β,γ-unsaturated carbonyl compounds. The present protocol exhibits perfect atom economy in the allylation step and is characterized by a great functional group compatibility. Furthermore, the use of α-substituted malononitriles allowed for the construction of all-carbon quaternary centers.
- Grugel, Christian P.,Breit, Bernhard
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supporting information
p. 15223 - 15226
(2018/09/25)
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- A Practical Three-Step Synthesis of Vinylferrocene
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An improved, short and efficient synthesis of vinylferrocene is reported. This three-step synthesis includes Friedel-Crafts acylation, reduction, and a one-pot mesylation/elimination step to afford the target compound in 62% yield over three steps.
- Plevová, Kristína,Mudráková, Brigita,?ebesta, Radovan
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p. 760 - 763
(2017/12/26)
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- Synthesis, characterization and second-order nonlinear optical behaviour of ferrocene-diketopyrrolopyrrole dyads: The effect of alkene: Vs. alkyne linkers
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New, thermally stable dipolar ferrocene-diketopyrrolopyrrole (Fc-DPP) dyads with alkene as a linker exhibited structure dependent first hyperpolarizabilities, βHRS, recorded by a femtosecond HRS technique using a femtosecond (120 fs) pulsed laser light system at 900 nm at ambient temperature. On the basis of linear optical, electrochemical and TD-DFT studies, a good structure-polarization relationship has been established to account for the observed trends in first hyperpolarizabilities. The dyads exhibited fluctuating but matching solvatochromism. Nonlinear optical properties are modulated both by the strength of the acceptor as well as the length and nature of the π-conjugation bridge. βHRS of the dyads were compared with structurally related dyads in which the DPP core and the Fc donor are linked via an alkyne bridge. It is interesting to observe that the replacement of an alkyne link with alkene in these D-π-A chromophores does not necessarily furnish enhanced βHRS.
- Kaur, Sarbjeet,Van Steerteghem, Nick,Kaur, Paramjit,Clays, Koen,Singh, Kamaljit
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p. 9717 - 9726
(2016/11/02)
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- A PHOTO-CLEAVABLE MASS TAG AND USE OF THE SAME
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The present invention refers to photo-degradable relates to of the present invention and use thereof markers mass markers mass photo-degradable biomarker-of detecting and quantifying analysis may be utilized, multiple marker synchronous detection of ID. (by machine translation)
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Paragraph 0052; 0054; 0063; 0064
(2016/10/07)
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- Synthesis of esters of metallocene alcohols and 4,5-dichloroisothiazol-3-carboxylic and 5-arylisoxazole-3-carboxylic acids
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Acylation of alkyl- and 1,1′-dialkylferrocene alcohols and diols as well as (3,4,4-trichlorobut-3-ene-1-ol-1-yl)-4,5-cymantrene with dichloroisothiazole- and 5-arylisoxazole-3-carbonyl chlorides has afforded esters containing 1,2-azoles fragments. Some of the obtained compounds have exhibited potentiating action in the binary mixtures with insecticides.
- Potkin,Dikusar,Kletskov,Petkevich,Semenova,Kolesnik,Zvereva,Zhukovskaya,Rosentsveig,Levkovskaya,Zolotar
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p. 338 - 343
(2016/04/20)
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- Ferrocenylalkylation of 2-mercaptobenzoxazoles
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Regioselectivity of the HBF4-catalyzed ferrocenylalkylation of 2-mercaptobenzoxazole in two phase aqueous organic solvent mixture was studied. The reaction proceeds regioselectively at the heterocyclic nitrogen atom. Structures of the synthesiz
- Osipova, E. Yu.,Ivanova,Rodionov,Korlyukov,Arkhipov,Simenel
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p. 2868 - 2872
(2017/06/05)
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- Cobalt-catalyzed asymmetric hydroboration of aryl ketones with pinacolborane
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The highly enantioselective cobalt-catalyzed hydroboration reaction of aryl ketones with HBpin was developed using iminopyridine oxazoline ligands. Halides, amines, ethers, sulfides, esters and amides are well tolerated under the mild reaction conditions, demonstrating its synthetic advantage. Substituted diaryl ketones could also be hydroborated with high enantioselectivity.
- Guo, Jun,Chen, Jianhui,Lu, Zhan
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supporting information
p. 5725 - 5727
(2015/03/30)
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- Ruthenium-Catalyzed Enantioselective Hydrogenation of Ferrocenyl Ketones: A Synthetic Method for Chiral Ferrocenyl Alcohols
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Highly effective asymmetric hydrogenation of various ferrocenyl ketones, including aliphatic ferrocenyl ketones as well as the more challenging aryl ferrocenyl ketones, was realized in the presence of a Ru/diphosphine/diamine bifunctional catalytic system. Excellent enantioselectivities (up to 99.8% ee) and activities (S/C = 5000) could be obtained. These asymmetric hydrogenations provided a convenient and efficient synthetic method for chiral ferrocenyl alcohols, which are key intermediates for a variety of chiral ferrocenyl ligands and resolving reagents.
- Lu, Bin,Wang, Qun,Zhao, Mengmeng,Xie, Xiaomin,Zhang, Zhaoguo
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p. 9563 - 9569
(2015/10/12)
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- Hydrosilylation of aldehydes and ketones catalyzed by half-sandwich manganese(I) N-heterocyclic carbene complexes
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Easily available manganese(I) N-heterocyclic carbene (NHC) complexes, Cp(CO)2Mn(NHC), obtained in one step from industrially produced cymantrene, were evaluated as pre-catalysts in the hydrosilylation of carbonyl compounds under UV irradiation. Complexes with NHC ligands incorporating at least one mesityl group led to the most active and selective catalytic systems. A variety of aldehydes (13 examples) and ketones (11 examples) were efficiently reduced under mild conditions [Cp(CO)2Mn(IMes) (1 mol%), Ph 2SiH2 (1.5 equiv.), hν (350 nm), toluene, 25 °C, 1-24 h] with good functional group tolerance.
- Zheng, Jianxia,Elangovan, Saravanakumar,Valyaev, Dmitry A.,Brousses, Remy,Cesar, Vincent,Sortais, Jean-Baptiste,Darcel, Christophe,Lugan, Noel,Lavigne, Guy
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supporting information
p. 1093 - 1097
(2014/04/03)
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- A versatile electrochemical sensing receptor based on a molecularly imprinted polymer
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Electrochemical molecularly imprinted polymers (e-MIPs) are reported for the first time. Their elaboration is based on the introduction of a redox tracer (vinylferrocene) inside the binding cavities of a cross-linked MIP. Determination of the analyte (benzo[a]pyrene) can be simply performed by measuring the redox tracer signal. the Partner Organisations 2014.
- Udomsap, Dutduan,Branger, Catherine,Culioli, Gérald,Dollet, Pascal,Brisset, Hugues
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supporting information
p. 7488 - 7491
(2014/07/07)
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- Tuneable superbase-catalyzed vinylation of α-hydroxyalkylferrocenes with alkynes
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Superbase-catalyzed (KOH/DMSO suspension as a catalyst) vinylation of hydroxymethyl- and hydroxyethylferrocenes with terminal and internal alkynes (acetylene, propyne, phenylacetylene, 3-ethynylpyridine, 1-propyn-1-yl-benzene, diphenylacetylene) affords hitherto unknown vinyl ethers of ferrocene in 30-93% yields depending on the alkyne structure and the tuneable ratio of reactants/KOH/DMSO. The vinylation smoothly proceeds under mild conditions (70-90 °C, 0.25-13 h). With unsubstituted acetylene the process is readily realized under atmospheric pressure (yield of the corresponding vinyl ethers is 81-90%) though under pressure (initial pressure at room temperature is 10-13 atm, maximum pressure is 13-16 atm at the reaction temperature) the yield is close to quantitative (93%). The synthesized compounds were characterized using 1H and 13C NMR, and IR spectroscopy, as well as X-ray diffraction analysis.
- Trofimov, Boris A.,Oparina, Ludmila A.,Tarasova, Olga A.,Artem'ev, Alexander V.,Kobychev, Vladimir B.,Gatilov, Yuriy V.,Albanov, Alexander I.,Gusarova, Nina K.
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p. 5954 - 5960
(2015/03/30)
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- A convenient nickel-catalysed hydrosilylation of carbonyl derivatives
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Hydrosilylation of aldehydes and ketones catalysed by nickel acetate and tricyclohexylphosphine as the catalytic system was demonstrated using polymethylhydrosiloxane as a cheap reducing reagent. The Royal Society of Chemistry 2013.
- Zheng, Jianxia,Darcel, Christophe,Sortais, Jean-Baptiste
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- Synthesis and biological evaluation of novel ferrocene-naphthoquinones as antiplasmodial agents
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This work deals with the synthesis and evaluation of new compounds designed by combination of 1,4-naphthoquinone and ferrocene fragments in a 3-ferrocenylmethyl-2-hydroxy-1,4-naphthoquinone arrangement. A practical coupling reaction between 2-hydroxy-1,4-naphthoquinone and ferrocenemethanol derivatives has been developed. This procedure can be carried out "on-water", at moderate temperatures and without auxiliaries or catalysts, with moderate to high yields. The synthesized derivatives have shown significant in vitro antiplasmodial activity against chloroquine-sensitive and resistant Plasmodium falciparum strains and it has been shown that this activity is not related to the inhibition of biomineralization of ferriprotoporphyrin IX. Binding energy calculations and docking of these compounds to cytochrome b in comparison with atovaquone have been performed.
- García-Barrantes, Pedro M.,Lamoureux, Guy V.,Pérez, Alice L.,García-Sánchez, Rory N.,Martínez, Antonio R.,San Feliciano, Arturo
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p. 548 - 557
(2013/12/04)
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- Synthesis, structure, and reactivity of ferrocenyl-NHC palladium complexes
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palladium complexes of ferrocenyl-functionalized N-heterocyclic carbenes with different substituents were synthesized. The molecular structures of selected complexes were determined by X-ray diffraction and show a pseudo-square-planar structure with a central palladium atom surrounded by carbene, pyridine, and two chloride ligands. The influence of the different substituents on the structure and reactivity of the complexes was studied. The catalytic properties of the complexes were investigated in the Larock indolization reactions of 2-bromoanilines with diphenylacetylene. Their performances slightly varied in this reaction, but the complex with mesityl substituent showed the best activity. Copyright
- He, Pan,Du, Yufeng,Wang, Shuzhan,Cao, Changsheng,Wang, Xiaojun,Pang, Guangsheng,Shi, Yanhui
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p. 1004 - 1010
(2013/07/28)
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- Palladium-catalyzed reaction of 2-iodoferrocenyl alcohols with internal alkynes: Synthesis of functionally 1,2-disubstituted ferrocenes and ferroceno-pyrans
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The reaction of racemic (2-iodoferrocenyl)methanol with internal alkynes in the presence of (dppf)PdCl2 and i-Pr2NH produces alkenyl-substituted ferrocene carboxaldehydes in moderate yields. All reactions are carried out at 100 or 120 °C for different reaction times (between 6 and 26 h) in a screw-cap Pyrex bottle. The scope and limitations of this reaction are studied by employing variously substituted 11 internal alkynes. The reactions are regioselective with alkynes having a sterically crowded substituent such as t-butyl and trimethylsilyl groups. Moreover, racemic 1-(2-iodoferrocenyl)ethanol derivatives are synthesized as two diastereomers. Both diastereomers are reacted with internal alkynes in the presence of (dppf)PdCl2 and i-Pr2NH at 120 °C to afford alkenyl-substituted acetylferrocenes and ferroceno-pyrans in moderate to good yields. According to the alkyne employed, different reaction times (between 6 and 55 h) are necessary to drive the reactions to completion. Mechanisms are also suggested for the formation of observed products.
- Yucel, Baris,Sanli, Bahar,Soylemez, Huseyin,Akbulut, Huseyin
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- Hydrosilylation of aldehydes and ketones catalyzed by an n-heterocyclic carbene-nickel hydride complex under mild onditions
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Half-sandwich N-heterocyclic carbene (NHC)-nickel complexes of the general formula [NiACHTUNGTRENUNG(NHC)ClCp?] (Cp?= Cp, Cp*) efficiently catalyze the hydrosilylation of aldehydes and ketones at room temperature in the presence of a catalytic amount of sodium triethylborohydride and thus join the fairly exclusive club of well-defined nickel(II) catalyst precursors for the hydrosilylation of carbonyl functionalities. Of notable interest is the isolation of an intermediate nickel hydride complex that proved to be the real catalyst precursor.
- Bheeter, Linus P.,Henrion, Mickael,Brelot, Lydia,Darcel, Christophe,Chetcuti, Michael J.,Sortais, Jean-Baptiste,Ritleng, Vincent
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supporting information
p. 2619 - 2624
(2013/01/15)
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- PALLADIUM CATALYSTS
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The invention relates to a particulate substance comprising a particulate porous support coupled to a palladium species. The palladium species may comprise palladium nanoclusters. The particulate substance may be used as a catalyst for conducting a carbon-carbon coupling reaction or a reduction.
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Page/Page column 14; 19
(2010/05/13)
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- RUTHENIUM CATALYSTS FOR CATALYTIC HYDROGENATION
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The present disclosure relates to a process for the hydrogenation of compounds comprising one or more carbon-oxygen (C═O) double bonds, to provide the corresponding alcohol, comprising contacting the compound with hydrogen gas at and a catalyst comprising a ruthenium-aryl-aminophosphine complex.
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Page/Page column 6-8
(2009/02/11)
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- Modified hydroborate agent: (2,2′-bipyridyl)(tetrahydroborato)zinc complex, [Zn(BH4)2(bpy)], as a new, stable, efficient ligand-metal hydroborate and chemoselective reducing agent
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(2,2′-Bipyridyl)(tetrahydroborato)zinc complex, [Zn(BH4)2(bpy)], is a new white stable compound which has been used for efficient reduction of variety of carbonyl compounds such as aldehydes, ketones, acyloins, α-diketones and α, β-unsaturated carbonyl compounds (1,2-reduction) to their corresponding alcohols in acetonitrile at room temperature. Excellent chemoselectivity was also observed for the reduction of aldehydes over ketones with this reducing agent.
- Zeynizadeh, Behzad
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p. 317 - 326
(2007/10/03)
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- Efficient regio- and diastereo-controlled synthesis of 1,1′- and 1,1′,2,2′-functionalised ferrocenes and the formation of 2-oxa[3]ferrocenophanes
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The synthesis of a C2 symmetric 1,1′ ,2,2′-tetrasubstituted ferrocene system was discussed. The route involved the reduction of ferrocenyl carbonyl compounds which gave access to a range of alcohols, alkenes, alkanes, ethers, and 2-oxa[3]ferrocenophanes depending on the precise conditions used. The loss of optical activity of 1,1′-bis(hydroxymethyl)ferrocenes and 1,1′-bis(hydroxymethyl)ruthenocenes, which had been prepared by asymmetric reduction, was demonstrated in an acidic medium by extensive 1H NMR studies.
- Carroll, Michael A.,White, Andrew J.P.,Widdowson, David A.,Williams, David J.
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p. 1551 - 1557
(2008/10/08)
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- The reactions of acylferrocenes with samarium diiodide: Reduction, deoxygenation, reductive coupling and rearrangement
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Acylferrocenes reacted with samarium diiodide in the presence of water to give the corresponding (α-hydroxyalkyl)ferrocenes or alkylferrocenes depending on the reaction time and temperature. On treatment with samarium diiodide in the absence of water, ferrocenecarbaldehyde underwent a reductive coupling to give pinacols, whereas acetylferrocene yielded 3,3-diferrocenyl-2-butanone and 2,3-diferrocenyl-2-butene via the subsequent rearrangement and deoxygenation.
- Jong, Shean-Jeng,Fang, Jim-Min,Lin, Chun-Hsu
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- α-Ferrocenylation of Tetrazole and Its 1-substituted Derivatives in Two-Phase Systems
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Reactions of α-ferrocenylalkyl alcohols with tetrazole and its 1-substituted derivatives in two-phase systems of methylene chloride-aqueous solutions of HX acids (X = BF4, ClO4) result in the formation of 4-α-ferrocenylalkylated tetrazolium salts as the only isomers. Under the action of alkali reagents in aqueous media monosubstituted tetrazolium salts are converted into mixtures of 1- and 2-α-ferrocenylalkyl tetrazole derivatives, while disubstituted salts decompose to give the starting compounds when heated in 10% aqueous solution of sodium hydroxide. In the anhydrous medium, heating of 1-phenyl-5-ferrocenylmethylenetetrazolium fluoborate with t-BuOK in dioxane results in a rearrangement which proceeds by an ilide-type mechanism to form 1-phenyl-5-ferrocenylmethylenetetrazole. The latter reacts in the two-phase system with ferrocenylmethanol to give the corresponding trisubstituted tetrazolium salt.
- Boev,Krasnikova,Moskalenko,Pil'ko,Snegur,Babin,Nekrasov
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p. 1299 - 1305
(2007/10/03)
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- Ferrocene compounds XXIII. Synthesis and reactions of the new type of methyl ferrocyloxyalkanoates
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The new types of ferrocenyloxaaliphatic acid ester, FcCHROCHR′COOMe (R = H, Me, Ph; R′ = H, Me) (7) have been prepared by the action of alkoxides derived from methyl glycolate or methyl lactate on the corresponding ferrocenylcarbinyl acetates (2) or N,N,N-trimethylferrocylammonium iodides (4). The esters obtained were accompanied by a small quantity of oligomeric esters, FcCHR(OCHR′CO)nOMe (9), and with more or less ferrocyl methyl ethers (8). As opposed to the alkaline hydrolysis of the analogous methyl benzoxyacetate (6) into benzoxyacetic acid (5) the acidification of sodium alkanoates 10 obtained by saponification of esters 7 gave unexpectedly the corresponding ferrocenylcarbinols 1. In a similar way the esters 7 were converted into mixtures of the mentioned carbinols and diferrocyl ethers 11 under action of aqueous hydrochloric acid. The mechanisms of the reactions 10 → 1 and 7 → 1, 11 are discussed.
- Kovac,Rapic,Susnik,Suprina
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p. 149 - 158
(2007/10/03)
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- FERROCENYLTRITHIOCARBONATES I. DIRECT ACCESS FROM α-FERROCENYLCARBINOLS BY A SNi MECHANISM. ABSOLUTE X-RAY STRUCTURE DETERMINATION OF (R)-FERROCENYLMETHYLMETHANE S-METHYLTRITHIOCARBONATE
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Ferrocenyltrithiocarbonates (I) are readily obtained by treating α-ferrocenylcarbinols (II) successively with sodium hydride, carbon disulfide and alkyl halide.Formation of I occurs by intramolecular nucleophilic displacement of oxygen by sulfur with retention of configuration.This is supported by the nature of the other products formed and by the X-ray structure determination of an optically active compound I, which was refined to R = 0.038.The title compound of R configuration was obtained from (R)-ferrocenylmethylmethanol.
- Patin, Henri,Mignani, Gerard,Mahe, Christian,Marouille, Jean-Yves Le,Benoit, Alain,Grandjean, Daniel
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