- The evolution of reactive ligands in the catalysis of radical processes by copper complexes
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Two radical reactions (addition of CCl4 to the double bond of oct-1-ene and oxidation of dodecane-1-thiol with air oxygen) catalyzed by copper complexes have been investigated. Various nitrogen-containing compounds (aliphatic and aromatic amines, aminoalcohols, aminoacids) were used as the ligands. In both cases, products of ligand transformation have been observed, products of the transformations have been identified by GLC-MS. In case of the CCl4 addition, the reaction can be initiated by the either copper complex or the ligand. In case of the thiol coupling, the reaction proceeds as a conjugated oxidation of both the thiol and the ligand. A correlation between the donor ability of the ligand and its reactivity has been found. Copyright Taylor and Francis Group, LLC.
- Tarkhanova,Gantman,Rostovschikova
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- The addition of halogenocarbons to alkenes in the presence of (R = H, Me), and 2CH2>
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The addition of halogenocarbons to alkenes in the presence of (I) has been the subject of a detailed kinetic study.These results, together with the results of cross-over addition reactions of a halogenocarbon mixture and cross-over studies on catalyst mixtures of (I) and (IV) are interpreted in favour of a mechanism involving catalysis by an intact binuclear complex, but which also involves free radical intermediates.Studies on catalysis by (II) additional to those we reported earlier, suggest an analogous mechanism in this case, but also involving CO dissociation from the hexacarbonyl yielding IV as the active catalyst.A preliminary study of catalysis by 2CH2> (III) suggests this complex also follows a similar mechanism.
- Davis, Reg,Khazal, Nasser M.S.,Bitterwolf, Thomas E.
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- Atom Transfer Radical Addition Catalyzed by Ruthenium-Arene Complexes Bearing a Hybrid Phosphine-Diene Ligand
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The synthesis and characterization of a series of arene ruthenium complexes bearing either (3,5-cycloheptadienyl)diphenylphosphine or (cycloheptyl)diphenylphosphine are reported. Upon irradiation or heating, all these complexes lose their arene ligand but then exhibit a different behavior depending on the nature of the phosphine ligand. (Cycloheptadienyl)phosphine complexes 1 and 3 give a cationic dinuclear Ru complex 5 for which the two Ru atoms are bridged by three chlorido ligands and flanked by two tridendate (cycloheptadienyl)phosphines. (Cycloheptyl)diphenylphosphine complexes 2 and 4 undergo arene exchange when toluene is used as solvent or degrade in dichloromethane. ATRA catalytic trials conducted in parallel with these complexes using CCl4 and styrene as standard substrates, highlighted the deep impact of the dienyl moiety on the results. Under smooth conditions (UV irradiation or moderate heating), only (cycloheptyl)phosphine derivatives give Karasch adduct in satisfactory yields. Their performance was considerably improved by combining irradiation and heating. At higher temperature, cationic dinuclear complex 5 was revealed as active and robust, giving turnover numbers as high as 9700 when tetradecene and CCl4 were used as substrates.
- Chotard, Florian,Malacea-Kabbara, Raluca,Balan, Cédric,Bodio, Ewen,Picquet, Michel,Richard, Philippe,Ponce-Vargas, Miguel,Fleurat-Lessard, Paul,Le Gendre, Pierre
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- Addition of α-polyhalides to olefins under mild reaction conditions, catalyzed by Mo(CO)6
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Mo(CO)6 was found to be an efficient pre-catalyst in the 1,2-addition reaction of α-polyhalides to various olefins. Significantly, the reaction was run under mild conditions, viz. refluxing acetonitrile, with satisfactory yields. Cr(CO)6/
- Shvo, Youval,Green, Revital
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- Studies on sulfinatodehalogenation: The addition reaction of halocarbons with olefins initiated by sodium dithionite
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Halocarbons such as carbon tetrachloride, CCl3Br, CF3CCl3, BrCF2CF2Br, BrCF2CFClBr and CF2Br2, reacted with olefins in the presence of the sulfinatodehalogenation reagent sodium dithionite under mild conditions to give the corresponding adducts. In the case of F113, CFCl2CF2CFCl2 and CF3Cl3, the polyfluoroalkylation product resulted.
- Wu,Huang
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- The Reaction of Polyhalides with Allylsilanes Catalyzed by Copper(I) Chloride
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Allyltrimethylsilane reacted with polyhalogen compounds in the presence of copper species, such as copper(I) chloride, copper(II) chloride or metallic copper, to form polyhalo compounds containing an allyl group. Other allylsilane derivatives than allyltrimethylsilane were also subjected to a reaction with carbon tetrachloride. 3-Chloro- or 3-bromo-3-trimethylsilyl-1-propene gave 4,4,4-trichloro-1-trimethylsilyl-1-butene. Ethyl 1-trimethylsilylallyl carbonate afforded ethyl 4,4,4-trichloro-1-butenyl carbonate along with a hydrotrichloromethylation product. 2-Methyl-3-trimethylsilyl-1-propene yielded a product based on the addition of a trichloromethyl group followed by hydrogen-elimination from a 2-methyl group.
- Mitani, Michiharu,Hujita, Shigenori
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- From atom transfer radical addition to atom transfer radical polymerisation of vinyl monomers mediated by ruthenium indenylidene complexes
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Ruthenium indenylidene complexes provide a new class of versatile catalysts for promoting the Atom Transfer Radical Addition (ATRA) of carbon tetrachloride and chloroform toward a whole array of olefins such as acrylates, methacrylates, styrene and 1-octene. The reaction was successfully extended to an Atom Transfer Radical Polymerisation (ATRP) process by changing the monomer/halide ratio. The polymerisation reaction can be accelerated by adding n-Bu2NH to the reaction mixture. However this leads to an uncontrolled polymerisation. Further improvements to the catalytic activity can be made by transforming the Ru complexes in the cationic 14-electron species or exchanging the indenylidene fragment with an ethoxycarbene. A very high activity is reached when these complexes are exposed to methyl methacrylate in aqueous media while maintaining excellent control over the formed polymers.
- Opstal, Tom,Verpoort, Francis
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- New and improved catalysts for transition metal catalysed radical reactions
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New CuI and FeII complexes displayed considerable improvements in atom transfer radical addition reactions.
- De Campo, Floryan,Lastecoueres, Dominique,Verlhac, Jean-Baptiste
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- The addition of halogenocarbons to alkenes in the presence of and related complexes
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A kinetic study has been made of the addition of halogenocarbons to alkenes in the presence of (I).The results, together with the results of cross-over addition reactions of a halogenocarbon mixture and cross-over studies on catalyst mixtures of I and (II) have been interpreted in terms of a mechanism which involves catalysis by an intact dinuclear species, probably , but which also involves free radical intermediates.
- Davis, Reg,Durrant, Jim L. A.,Khazal, Nasser M. S.,Bitterwolf, Thomas E.
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- Structural and Electronic Noninnocence of α-Diimine Ligands on Niobium for Reductive C-Cl Bond Activation and Catalytic Radical Addition Reactions
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A d0 niobium(V) complex, NbCl3(α-diimine) (1a), supported by a dianionic redox-active N,N′-bis(2,6-diisopropylphenyl)-1,4-diaza-2,3-dimethyl-1,3-butadiene (α-diimine) ligand (ene-diamido ligand) served as a catalyst for radical addition reactions of CCl4 to α-olefins and cyclic alkenes, selectively affording 1:1 radical addition products in a regioselective manner. During the catalytic reaction, the α-diimine ligand smoothly released and stored an electron to control the oxidation state of the niobium center by changing between an η4-(σ2,π) coordination mode with a folded MN2C2 metallacycle and a κ2-(N,N′) coordination mode with a planar MN2C2 metallacycle. Kinetic studies of the catalytic reaction elucidated the reaction order in the catalytic cycle: the radical addition reaction rate obeyed first-order kinetics that were dependent on the concentrations of the catalyst, styrene, and CCl4, while a saturation effect was observed at a high CCl4 concentration. In the presence of excess amounts of styrene, styrene coordinated in an η2-olefinic manner to the niobium center to decrease the reaction rate. No observation of oligomers or polymers of styrene and high stereoselectivity for the radical addition reaction of CCl4 to cyclopentene suggested that the C-C bond formation proceeded inside the coordination sphere of niobium, which was in good accordance with the negative entropy value of the radical addition reaction. Furthermore, reaction of 1a with (bromomethyl)cyclopropane confirmed that both the C-Br bond activation and formation proceeded on the α-diimine-coordinated niobium center during transformation of the cyclopropylmethyl radical to a homoallyl radical. With regard to the reaction mechanism, we detected and isolated NbCl4(α-diimine) (6a) as a transient one-electron oxidized species of 1a during reductive cleavage of the C-X bonds; in addition, the monoanionic α-diimine ligand of 6a adopted a monoanionic canonical form with selective one-electron oxidation of the dianionic ene-diamido form of the ligand in 1a.
- Nishiyama, Haruka,Ikeda, Hideaki,Saito, Teruhiko,Kriegel, Benjamin,Tsurugi, Hayato,Arnold, John,Mashima, Kazushi
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- Electrochemistry as a correlation tool with the catalytic activities in [RuCl2(p-cymene)(PAr3)]-catalysed Kharasch additions
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[RuCl2(p-cymene)] complexes containing triarylphosphine ligands with various substituents at the para position were used to catalyse the atom transfer radical addition of carbon tetrachloride to various olefins, and their catalytic activities were nicely correlated with their electrochemical parameters.
- Richel, Aurore,Demonceau, Albert,Noels, Alfred F.
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- Addition Reaction of Polychloro Compounds to Carbon-Carbon Multiple Bonds Catalyzed by Semiconductor Particles under Photoirradiation
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Polychloro compounds were added to olefins in the presence of semiconductor particles (TiO2 or CdS) under photoirradiation.The photoreaction without semiconductors afforded no adducts at all; however, loading of TiO2 with Ag, Cu, or Fe3O4 enhanced the yield of the photoaddition reaction even further.Semiconductors operate as catalysts for the one-electron injection into the polychloro compounds.The relative adsorptions of the polychloro compounds onto the semiconductor particles correlate with the yields of the adducts, while the half-wave reduction potentials of the polychlorides do not.This semiconductor-catalyzed reaction was selective to unfunctionalized olefins and to those bearing a functional group at a remote position.An alkyne furnished the product via further reduction following addition, i.e., 1,1,3-trichloro-1-heptene (7) from 1-hexyne and carbon tetrachloride.
- Mitani, Michiharu,Kiriyama, Takuya,Kuratate, Tomoaki
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- THE MECHANISM OF THE ADDITION OF TETRAHALOALKANES TO ALKENES IN THE PRESENCE OF RuCl2(PPh3)3
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The addition of tetrahaloalkanes to alkenes in the presence of has been examined in detail and it is suggested that it proceeds by a non-chain catalysed mechanism involving free radical intermediates.
- Bland, William J.,Davis, Reg,Durrant, Jim L. A.
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- Addition of Halogenocarbons or Dihydrogen to Alkenes in the Presence of : Catalysis by a Dinuclear Species
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Addition of halogenocarbons or dihydrogen to alkenes in the presence of (1) has been shown to proceed by a non-radical catalytic cycle in which a dinuclear species, probably , is the active catalyst.
- Davis, Reg,Khazaal, Nasser M. S.,Maistry, Vishnu
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- Copper-catalyzed atom transfer radical addition (ATRA) and cyclization (ATRC) reactions in the presence of environmentally benign ascorbic acid as a reducing agent
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In recent years, copper-catalyzed atom transfer radical addition (ATRA) has emerged as a viable organic procedure for the formation of carbon-carbon bonds starting from alkyl halides and alkenes. Studies have primarily focused on the use of free-radical initiators to regenerate the copper(i) complex or activator in situ. Although these initiators led to a significant decrease in the amount of metal catalyst, they were much less effective for highly active alkenes that readily undergo free-radical polymerization. In this study, the non-radical reducing agent ascorbic acid (commonly known as Vitamin C) was effectively employed resulting in TONs as high as 15200 in the homogenous ATRA of polyhalogenated compounds to α-olefins, and enabling selective monoadduct formation for highly active alkenes such as acrylonitrile (TONs as high as 11800). As low as 7-20 mol% of ascorbic acid relative to substrate was sufficient for all ATRA and ATRC reactions examined. Further, product isolations for all selected syntheses were quite facile and nearly quantitative, requiring only simple liquid-liquid extraction techniques. Reactions in the presence of ascorbic acid were also examined kinetically via1H NMR and UV/Vis spectroscopy. A half order rate dependence on reducing agent concentration was observed, but the first order kinetic plots became nonlinear as the concentration of ascorbic acid was increased. Finally, the use of ascorbic acid circumvented otherwise necessary purging techniques, successfully furthering the utility of these reactions in organic synthesis.
- Taylor, Matthew J. W.,Eckenhoff, William T.,Pintauer, Tomislav
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- Hydration of alkenes and cycloalkenes in the presence of chromium and copper complexes
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Chromium and copper complexes catalyzed hydration of acyclic and cyclic olefins in the presence of carbon tetrachloride at 110-160 C (4-12 h) with formation of the corresponding alcohols.
- Khusnutdinov,Oshnyakova,Shchadneva
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- Adsorption and catalytic conversion of hydrocarbons on nanosized gold particles immobilized on alumina
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Gold and nickel particles immobilized on alumina were prepared by the metal vapor synthesis and anionic adsorption methods. The dispersion of metals was determined by X-ray diffraction and transmission electron microscopy. The activity of nanoparticles, tested in model catalytic reactions of CCl 4 addition to multiple bonds and allyl isomerization of allylbenzene, changes in a wide range (from 1 to 3000 (mole of product) (mole of Au) -1 h-1) and is parallel to the chromatographically measured heats of adsorption of the corresponding unsaturated substrates. The heat of adsorption of unsaturated hydrocarbons can serve as a criterion for the efficiency of the gold-containing catalyst in olefin conversion.
- Smirnov,Lanin,Vasil'kov,Nikolaev,Murav'eva,Tyurina,Vlasenko
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- The mechanism of the addition of haloalkanes to alkenes in the presence of and
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Kinetic and other studies have demonstrated that the addition of haloalkanes to alkenes in the presence of either or has a mechanism very similar to that observed in the presence of .The previous report of enhanced catalytic activity for the two hydrides has not been confirmed.
- Davis, Reg,Furze, John D.,Cole-Hamilton, David J.,Pogorzelec, Peter
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- Kharasch addition of tetrachloromethane to alkenes catalyzed by metal acetylacetonates
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Various transition metal acetylacetonates have proven to be efficient catalytic systems for the Kharasch addition of tetrachloromethane to alkenes under mild conditions, providing 1:1 adducts in up to 87% yield, based on internal standard. The nature of metal, solvent, temperature, olefin/CCl 4 ratio and the presence of nucleophilic co-catalysts were tested to evaluate the scope and limitation of the reaction.
- Boualy, Brahim,Harrad, Mohamed Anouar,El Firdoussi, Larbi,Ait Ali, Mustapha,El Houssame, Soufiane,Karim, Abdellah
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- A half-sandwich 1,2-azaborolyl ruthenium complex: Synthesis, characterization, and evaluation of its catalytic activities
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A half-sandwich 1,2-azaborolyl (Ab) ruthenium complex, (Ab-CCPh) RuCl(PPh3)2 (1), has been synthesized by treating RuCl2(PPh3)3 with lithium 1,2-azaborolide L-1, or by treating either RuCl2(PPh3)3 or RuHCl(PPh3)3 directly with 1,2-azaborole LH-1. It is evaluated as a suitable precatalyst in [2 + 2] cycloadditions of norbornene derivatives with DMAD and in atom transfer radical additions of halogenated compounds with olefins. The Royal Society of Chemistry.
- Liu, Zicheng,Xu, Junjie,Ruan, Wenqing,Fu, Chen,Zhang, Hui-Jun,Wen, Ting-Bin
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supporting information
p. 11976 - 11980
(2013/09/02)
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- Metal-free, radical addition to alkenes via desulfitative chlorine atom transfer
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An efficient method for radical additions to unactivated alkenes via desulfitative chlorine-atom transfer is described. The reaction is based on the use of readily available sulfonyl chlorides as starting materials and cheap radical initiators such as azobisisobutyronitrile (AIBN), di-tert-butyldiazene (DTBD), and dilauroyl peroxide (DLP). No transition metal catalyst is required and the reaction takes place under mild conditions at temperatures °C. Copyright
- Cao, Lidong,Weidner, Karin,Renaud, Philippe
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supporting information; experimental part
p. 3467 - 3472
(2012/02/03)
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- Atom transfer radical addition (ATRA) catalyzed by copper complexes with tris[2-(dimethylamino)ethyl]amine (Me6TREN) ligand in the presence of free-radical diazo initiator AIBN
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In this article, we focus on the evaluation of tris[2-(dimethylamino)ethyl] amine (Me6TREN) ligand in copper catalyzed ATRA in the presence of free-radical diazo initiator AIBN (2,2′-azobis(2-methylpropionitrile)). The addition of carbon tetrac
- Eckenhoff, William T.,Pintauer, Tomislav
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experimental part
p. 4909 - 4917
(2011/06/27)
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- An efficient, selective, and reducing agent-free copper catalyst for the atom-transfer radical addition of halo compounds to activated olefins
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Efficient and selective ATRA reactions of CCl4, CBr4, TsCl (Ts = tosyl), or Cl3CCO2Et with activated olefins (styrene, methyl methacrylate, n-butyl methacrylate, ferf-butyl methacrylate) using the TptBuCu(NCMe) complex as a catalyst have been achieved In the absence of any reductant and with low catalyst loadings.
- Munoz-Molina, Jose Maria,Belderrain, Tomas R.,Perez, Pedro J.
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experimental part
p. 642 - 645
(2010/03/25)
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- Highly efficient ambient-temperature copper-catalyzed atom-transfer radical addition (ATRA) in the presence of free-radical initiator (V-70) as a reducing agent
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Highly efficient, ambient-temperature, copper-catalyzed Atom Transfer Radical Addition (ATRA) of polyhalogenated compounds to alkenes in the presence of free radical initiator 2,2' -azobis (4-methoxy-2,4-dimethyl valeronitrile)(V-70)as a reducing agent was reported. The discrepancies between the alkene conversion and percent yield were mostly due to competing free-radical polymerization. ATRA of polyhalogenated compounds to monomers that are highly active in free-radical polymerization was not successful at 60 ° C when AIBN was used as radical initiator. The V-70 was proved to be very effective reducing agent, enabling selective formation of the monoadduct with α -olefins and highly active monomers such as methyl acrylate, methyl methacrylate, and vinyl acetate. The methodology for catalyst regeneration in copper-mediated ATRA in the presence of V-70 as a reducing agent also worked very well in the addition of CCl4 and CBr4 to highly active vinyl acetate.
- Pintauer, Tomislav,Eckenhoff, William T.,Ricardo, Carolynne,Balili, Marielle N. C.,Biernesser, Ashley B.,Noonan, Sean J.,Taylor, Matthew J. W.
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supporting information; experimental part
p. 38 - 41
(2009/06/17)
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- Addition of CCl4 to olefins catalyzed by chromium and ruthenium complexes: The influence of water as a nucleophilic additive
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The feasibility of the addition of CCl4 to linear and cyclic olefins and dienes in the presence of chromium and ruthenium complexes was established. The influence of water as a nucleophilic additive and the influence of the olefin nature, the c
- Khusnutdinov,Schadneva,Oshnyakova,Dzhemilev
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experimental part
p. 331 - 338
(2010/06/16)
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- Highly efficient heterogeneous aqueous Kharasch reaction with an amphiphilic resin-supported ruthenium catalyst
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An amphiphilic polystyrene-polyethylene glycol (PS-PEG) resin-supported ruthenium complex was designed and prepared. The polymeric Ru complex was found to promote the transition metal-catalyzed atom transfer radical addition of halogenated compounds to olefins, the Kharasch reaction, in water under heterogeneous as well as AIBN-free conditions with a high level of atom economy to meet green chemical requirements.
- Oea, Yohei,Uozumia, Yasuhiro
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experimental part
p. 1771 - 1775
(2009/07/09)
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- Addition of tetrachloromethane to oct-1-ene initiated by amino alcohols
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The kinetics and mechanism of an addition of CCl4 to oct-1-ene initiated by amines, aromatic alcohols, and amino alcohols (structural analogs of ephedrin) were studied. The radical mechanism of the reaction was established by ESR using the technique of spin traps. Aromatic amino alcohols as initiators are more active than amines and aromatic alcohols of similar structure. They are more selective compared to the amines and aromatic alcohols and react with CCl4 already at room temperature to form predominantly benzaldehyde. The scheme of initiation by aromatic amino alcohols of the addition of CCl 4 to olefins was proposed on the basis of the experimental data.
- Tarkhanova,Gantman,Chizhov,Smirnov
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p. 1624 - 1630
(2007/10/03)
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- Combinatorial catalysis with bimetallic complexes: Robust and efficient catalysts for atom-transfer radical additions
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A radical alternative? Two highly efficient catalysts for atom-transfer radical additions were discovered in a parallel screening of bimetallic complexes. Both catalysts contain a rhodium-centered fragment (blue), which is connected through three chloro bridges to a ruthenium-centered fragment (red).
- Quebatte, Laurent,Scopelliti, Rosario,Severin, Kay
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p. 1520 - 1524
(2007/10/03)
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- Atom transfer radical addition and enol-ester synthesis catalyzed by Ru-vinylidene complexes
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Ru-vinylidene complexes, Cl2Ru{=C=C(H)tBut}(PCy3)(L) (L=PCy3 or N-heterocyclic carbenes) reveal themselves as a versatile catalyst for the atom transfer radical addition (ATRA) of polyhalogenated alkanes to olefins, such as methylmethacrylate, styrene and 1-octene. Furthermore, these systems are excellent catalysts for the nucleophilic addition of carboxylic acids to terminal alkynes and yielded exclusively alk-1-en-2-yl esters. These complexes can also be transformed to their cationic counterparts by treating the neutral complexes with AgBF4 and their catalytic potential in ATRA and vinylation reaction are investigated.
- Opstal, Tom,Verpoort, Francis
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p. 9259 - 9263
(2007/10/03)
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- Addition of trichloromethyl radicals to alkenes: The use of phosphites as hydrogen-atom donors in intermolecular radical reactions
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Addition of trichloromethyl radicals (generated from BrCCl3 or CCl4) to a variety of alkenes in the presence of hydrogen-atom donors has been explored. The use of phosphites as hydrogen-atom donors was shown to provide a mild, novel and technically clean approach to trichloroalkanes.
- Barks,Gilbert,Parsons,Upeandran
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p. 1719 - 1722
(2007/10/03)
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- Kharasch addition and controlled atom transfer radical polymerisation (ATRP) of vinyl monomers catalysed by Grubbs' ruthenium-carbene complexes
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The Grubbs' ruthenium-carbene complexes, RuCl2(=CHPh)(PR3)2, mediate the Kharasch addition of CCl4 across olefins, and the controlled atom transfer radical polymerisation of vinyl monomers with high yields and selectivities which markedly depend on the phosphine ligands of the complex (R=phenyl, cyclopentyl, and cyclohexyl).
- Simal, Francois,Demonceau, Albert,Noels, Alfred F.
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p. 5689 - 5693
(2007/10/03)
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- The Fe0 promoted addition of CCl4 and CCl3Br to olefins
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The radical addition of CCl4 or CCl3Br to olefins is efficiently promoted by iron filings in N,N-dimethylformamide under mild conditions.
- Bellesia, Franco,Forti, Luca,Ghelfi, Franco,Pagnoni, Ugo M.
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p. 961 - 971
(2007/10/03)
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- Samarium Di-iodide Initiated Addition of Polyhalogenomethanes to Olefins
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Samarium di-iodide is different from other inorganic metallic salts, in the catalytic properties of the addition of polyhalogenomethanes to olefins.The reaction mechanism is briefly discussed.
- Ma, Shengming,Lu, Xiyan
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p. 2031 - 2033
(2007/10/02)
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- PALLADIUM-CATALYZED ADDITION REACTION OF OLEFINS, CARBON TETRACHLORIDE AND CARBON MONOXIDE IN ALCOHOLS TO GIVE 2-ALKYL-4,4,4-TRICHLOROBUTANOATES
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Pd(OAc)2 combined with PPh3 is good catalyst for the addition reaction of CCl4 and CO to olefins in ethanol to afford ethyl 2-alkyl-4,4,4-trichlorobutanoates.The esters were obtained in satisfactory yields when the reaction was carried out at 50 deg C in
- Tsuji, Jiro,Sato, Koji,Nagashima, Hideo
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p. 5003 - 5006
(2007/10/02)
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- ADDITION OF SULFONYL CHLORIDES TO OLEFINS IN THE PRESENCE OF CATALYTIC AMOUNTS OF DICHLOROTRIS(TRIPHENYLPHOSPHINE)RUTHENIUM(II)
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Reactions of sulfonyl chlorides with olefins catalysed by dichlorotris(triphenylphosphine)ruthenium(II) have been studied.Methanesulfonyl and arenesulfonyl chlorides added to 1-alkenes to give 1 : 1 adducts in high yields.Telomer formation is not observed, therefore the present reaction provides a general and convenient method for synthesis of β-chlorosulfones.A radical-chain mechanism is proposed for the reaction.
- Kamigata, Nobumasa,Sawada, Hideo,Suzuki, Norihiro,Kobayashi, Michio
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p. 199 - 204
(2007/10/02)
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- ACTIVATION OF POLYHALOALKANES BY PALLADIUM CATALYST. PREPARATION OF γ-TRICHLORO ESTERS BY COADDITION. REACTION OF CARBON TETRACHLORIDE AND CARBON MONOXIDE TO OLEFINS
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Pd(OAc)2 combined with PPh3 catalyzed the coaddition reaction of CCl4 and CO to olefins in ethanol to afford ethyl 2-alkyl-4,4,4-trichlorobutanoates.The best yields were obtained when the reaction was carried out in the presence of K2CO3 at low temperature.
- Tsuji, Jiro,Sato, Koji,Nagashima, Hideo
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p. 893 - 896
(2007/10/02)
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- The Reaction of Tetrachloromethane with Oct-1-ene in the Presence of 5-C5H5)2> and Other Transition-metal Complexes
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A study has been made of the mechanism of the addition reaction between CCl4 and oct-1-ene in the presence of 5-C5H5)2>.On the basis of kinetic and spectroscopic evidence and an examination of the reaction of some related model compo
- Davis, Reg,Groves, Ian F.
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p. 2281 - 2288
(2007/10/02)
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- METAL-OXIDE INDUCED REDOX CHAIN ADDITION OF TETRACHLOROMETHANE TO A CARBON-CARBON DOUBLE BOND
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Formation of 1:1 adducts in the addition of tetrachloromethane to a terminal carbon-carbon double bond was investigated at 76-200 deg C.The redox chain addition reaction with 1-octene, electron-deficient alkenes and unconjugated aliphatic dienes induced by catalytic amounts of copper(I) or copper(II) oxides in conjugation with diethylamine or diisopropylamine afforded the corresponding 1:1 adducts up to in 85percent yields.Aliphatic 1,3-dienes underwent redox chain 1,4-addition giving isomeric 1,1,1,5-tetrachloro-3-alkenes.
- Hajek, Milan,Silhavy, Premysl,Malek, Jaroslav
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p. 3488 - 3501
(2007/10/02)
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