- Studies on the interaction between poly-phosphane gold(I) complexes and dihydrofolate reductase: An interplay with nicotinamide adenine dinucleotide cofactor
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A class of gold(I) phosphane complexes have been identified as inhibitors of dihydrofolate reductase (DHFR) from E. coli, an enzyme that catalyzes the reduction of dihydrofolate (DHF) to tetrahydrofolate (THF), using NADPH as a coenzyme. In this work, to
- Pucciarelli, Stefania,Vincenzetti, Silvia,Ricciutelli, Massimo,Simon, Oumarou Camille,Ramadori, Anna Teresa,Luciani, Lorenzo,Galassi, Rossana
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Read Online
- Versatile Visible-Light-Driven Synthesis of Asymmetrical Phosphines and Phosphonium Salts
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Asymmetrically substituted tertiary phosphines and quaternary phosphonium salts are used extensively in applications throughout industry and academia. Despite their significance, classical methods to synthesize such compounds often demand either harsh reaction conditions, prefunctionalization of starting materials, highly sensitive organometallic reagents, or expensive transition-metal catalysts. Mild, practical methods thus remain elusive, despite being of great current interest. Herein, we describe a visible-light-driven method to form these products from secondary and primary phosphines. Using an inexpensive organic photocatalyst and blue-light irradiation, arylphosphines can be both alkylated and arylated using commercially available organohalides. In addition, the same organocatalyst can be used to transform white phosphorus (P4) directly into symmetrical aryl phosphines and phosphonium salts in a single reaction step, which has previously only been possible using precious metal catalysis.
- Arockiam, Percia Beatrice,Lennert, Ulrich,Graf, Christina,Rothfelder, Robin,Scott, Daniel J.,Fischer, Tillmann G.,Zeitler, Kirsten,Wolf, Robert
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supporting information
p. 16374 - 16382
(2020/11/03)
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- Ready Approach to Organophosphines from ArCl via Selective Cleavage of C-P Bonds by Sodium
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The preparation, application, and reaction mechanism of sodium phosphide R2PNa and other alkali metal phosphides R2PM (M = Li and K) have been studied. R2PNa could be prepared, accurately and selectively, via the reactions of SD (sodium finely dispersed in mineral oil) with phosphinites R2POR′ and chlorophosphines R2PCl. R2PNa could also be prepared from triarylphosphines and diarylphosphines via the selective cleavage of C-P bonds. Na was superior to Li and K for these reactions. R2PNa reacted with a variety of ArCl to efficiently produce R2PAr. ArCl is superior to ArBr and ArI since they only gave low yields of the products. In addition, Ph2PNa is superior to Ph2PLi and Ph2PK since Ph2PLi did not produce the coupling product with PhCl, while Ph2PK only gave a low yield of the product. An electron-withdrawing group on the benzene ring of ArCl greatly accelerated the reactions with R2PNa, while an alkyl group reduced the reactivity. Vinyl chloride and alkyl chlorides RCl also reacted efficiently. While t-BuCl did not produce the corresponding product, admantyl halides could give the corresponding phosphine in high yields. A wide range of phosphines were prepared by this method from the corresponding chlorides. Unsymmetric phosphines could also be conveniently generated in one pot starting from Ph3P. Chiral phosphines were also obtained in good yields from the reactions of menthyl chlorides with R2PNa. Possible mechanistic pathways were given for the reductive cleavage of R3P by sodium generating R2PNa and the substitution reactions of R2PNa with ArCl generating R2PAr.
- Ye, Jingjing,Zhang, Jian-Qiu,Saga, Yuta,Onozawa, Shunya,Kobayashi, Shu,Sato, Kazuhiko,Fukaya, Norihisa,Han, Li-Biao
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p. 2682 - 2694
(2020/07/30)
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- A practical synthesis of unsymmetrical triarylphosphines by heterogeneous palladium(0)-catalyzed cross-coupling of aryl iodides with diphenylphosphine
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The heterogeneous cross-coupling reaction of aryl iodides with diphenylphosphine was achieved in DMAc at 130 °C in the presence of 1.0 mol% of MCM-41-supported tridentate nitrogen palladium(0) complex [MCM-41-3N-Pd(0)] with KOAc as base, yielding a variety of unsymmetrical triarylphosphines in good to excellent yields. The turnover frequency (TOF) of the catalyst can reach 30.67 h?1. This new heterogeneous palladium(0) catalyst could easily be prepared by a simple procedure from commercially readily available reagents, and exhibited the same catalytic activity as homogeneous Pd(OAc)2 or Pd(PPh3)4, and could be recovered by filtration of the reaction solution and recycled at least seven times without significant loss of catalytic activity.
- Xu, Zhaotao,Wang, Pingping,Chen, Qiurong,Cai, Mingzhong
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- An efficient heterogeneous cross-coupling of aryl iodides with diphenylphosphine catalyzed by copper (I) immobilized in MCM-41
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The heterogeneous cross-coupling reaction of aryl iodides with diphenylphosphine was achieved in toluene at 115?°C in the presence of 10?mol% of phenanthroline-functionalized MCM-41-supported copper (I) complex (Phen-MCM-41-CuI) with Cs2CO3 as base, yielding various unsymmetric triarylphosphines in good to excellent yields. This protocol can tolerate a wide range of functional groups and does not need the use of expensive additives or harsh reaction conditions. This heterogeneous Cu (I) catalyst exhibited the same catalytic activity as homogeneous CuI/Phen system, and could easily be recovered by a simple filtration of the reaction solution and recycled up to seven times without significant loss of activity.
- Fang, Zhiqiang,Cai, Mingzhong,Lin, Yang,Zhao, Hong
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- Palladium-catalyzed C–P(III) bond formation reaction with acylphosphines as phosphorus source
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Palladium-catalyzed C–P(III) bond formation reaction employing acylphosphines as the phosphorus source was developed. Under the optimized conditions, acylphosphines could react with aryl halides directly affording trivalent phosphines in up to 94% yield.
- Yu, Rongrong,Chen, Xingyu,Wang, Zhiqian
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supporting information
p. 3404 - 3406
(2016/07/11)
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- Organocatalyzed Reduction of Tertiary Phosphine Oxides
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A novel selective catalytic reduction method of tertiary phosphine oxides to the corresponding phosphines has been developed. Notably, the reaction proceeds smoothly with low catalyst loadings of 1-5 mol% even at low temperature (70 C). Under the optimized conditions various phosphine oxides could be selectively reduced and the desired phosphines were usually obtained in excellent yields above 90%. Furthermore, we have developed a one-pot reaction sequence for the preparation of valuable phosphinborane adducts. Simple addition of BH3THF subsequent to the reduction step gave the desired adducts in yields up to 99%.
- Schirmer, Marie-Luis,Jopp, Stefan,Holz, Jens,Spannenberg, Anke,Werner, Thomas
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supporting information
p. 26 - 29
(2016/01/25)
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- A rhodium triphenylphosphine catalyst for alkene hydrogenation supported on neat superparamagnetic iron oxide nanoparticles
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A phosphonic acid functionalized triphenylphosphine rhodium complex was synthesized and grafted onto neat superparamagnetic iron oxide nanoparticles. The material was investigated by elemental analysis, IR spectroscopy, thermogravimetric analysis, XRD, N2-physisorption analyses, and TEM measurements. The obtained hybrid material could be used as a catalyst for the hydrogenation of alkenes with excellent yields and a broad substrate scope. The catalyst can be reused ten times without any loss of activity. According to the results from X-ray absorption spectroscopy, it is likely that formation of Rh nanoparticles occurs during the reaction.
- Dehe, Daniel,Wang, Lei,Müller, Melanie K.,D?rr, Gunder,Zhou, Zhou,Klupp-Taylor, Robin N.,Sun, Yu,Ernst, Stefan,Hartmann, Martin,Bauer, Matthias,Thiel, Werner R.
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p. 127 - 136
(2015/03/05)
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- A recyclable ruthenium(ii) complex supported on magnetic nanoparticles: A regioselective catalyst for alkyne-azide cycloaddition
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A magnetically separable ruthenium catalyst was synthesized through immobilizing a pentamethylcyclopentadienyl ruthenium complex on iron oxide nanoparticles. The catalyst is highly active and selective for the synthesis of 1,5-disubstituted 1,2,3-trizoles
- Wang, Dong,Salmon, Lionel,Ruiz, Jaime,Astruc, Didier
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p. 6956 - 6958
(2013/09/02)
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- Highly chemoselective metal-free reduction of phosphine oxides to phosphines
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Unprecedented chemoselective reductions of phosphine oxides to phosphines proceed smoothly in the presence of catalytic amounts of specific Br?nsted acids. By utilizing inexpensive silanes, e.g., PMHS or (EtO)2MeSiH, other reducible functional groups such as ketones, aldehydes, olefins, nitriles, and esters are well-tolerated under optimized conditions.
- Li, Yuehui,Lu, Liang-Qiu,Das, Shoubhik,Pisiewicz, Sabine,Junge, Kathrin,Beller, Matthias
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p. 18325 - 18329
(2013/01/15)
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- General and selective copper-catalyzed reduction of tertiary and secondary phosphine oxides: Convenient synthesis of phosphines
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Novel catalytic reductions of tertiary and secondary phosphine oxides to phosphines have been developed. Using tetramethyldisiloxane (TMDS) as a mild reducing agent in the presence of copper complexes, PO bonds are selectively reduced in the presence of other reducible functional groups (FGs) such as ketones, esters, and olefins. Based on this transformation, an efficient one pot reduction/phosphination domino sequence allows for the synthesis of a variety of functionalized aromatic and aliphatic phosphines in good yields.
- Li, Yuehui,Das, Shoubhik,Zhou, Shaolin,Junge, Kathrin,Beller, Matthias
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scheme or table
p. 9727 - 9732
(2012/07/14)
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- Fluoride catalyzed P-aryl-coupling - A mild approach to functionalized arylphosphines
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Functionalized triaryl- and diarylalkylphosphines are accessible in high yields following a mild fluoride catalyzed phosphorous-carbon coupling protocol starting from fluoroarenes and silylated phosphines. The reaction requires a minimum of solvent and ca
- Reis, Andreas,Dehe, Daniel,Farsadpour, Saeid,Munstein, Isabel,Sun,Thiel, Werner R.
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supporting information; experimental part
p. 2488 - 2495
(2012/01/04)
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- Novel phosphite palladium complexes and their application in C-P cross-coupling reactions
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A mono- and a 1,3-bis-phosphite arene ligand based on 2,2′-biphenol have been synthesized in order to study the synthesis of the corresponding palladium(II) complexes starting from different Pd precursors. Novel bis-phosphite palladium complex 1 [PdCl2(L)2] (L = dibenzo[d,f][1,3,2]dioxaphosphepin, 6-phenoxy), C,P-chelate bonded monophosphite palladium complex 2 [Pd(κ2-L)(μ-Cl)]2, and PCP-pincer palladium complex 3 have been prepared from these ligands in promising to excellent yields (50-95%). Additionally, complexes 1 and 3 have been characterized by X-ray crystal structure determinations. The application of 2,6-bis-phosphite pincer palladium(II) complex 3 in C-P cross-coupling between diphenylphosphine-borane and a wide range of various aryl iodides under very mild conditions is reported. Kinetic investigations indicate that 3 merely acts as a pre-catalyst and that Pd nanoparticles are the actual catalytically active species.
- Li, Jie,Lutz, Martin,Spek, Anthony L.,Van Klink, Gerard P.M.,Van Koten, Gerard,Klein Gebbink, Robertus J.M.
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experimental part
p. 2618 - 2628
(2010/11/21)
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- Synthesis of aryl phosphines via phosphination with triphenylphosphine by supported palladium catalysts
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The palladium catalyzed phosphination of functionalized aryl bromides, triflates, and chlorides with triphenylphosphine to yield aryldiphenylphosphines was catalyzed by thermally stable palladium catalysts supported on charcoal and aluminia. The addition
- Wang, Yanchun,Lai, Chi Wai,Kwong, Fuk Yee,Jia, Wen,Chan, Kin Shing
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p. 9433 - 9439
(2007/10/03)
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- Rhodium-Catalyzed Methylenation of Aldehydes
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The rhodium-catalyzed methylenation of aldehydes using trimethylsilyldiazomethane and triphenylphosphine produces a variety of terminal alkenes in excellent yields. These mild and nonbasic reaction conditions allow the conversion of enolizable substrates (keto aldehydes and nonracemic α-substituted aldehydes) to terminal alkenes without epimerization. Optimization of the reaction conditions led to the conclusion that a variety of rhodium(I) sources can be used as catalysts. The effect of the solvent on the reaction has also been studied, and it indicates that although the THF is the best solvent, other solvents may be used. The reactivity of the system is very much dependent on the nature of the phosphine reagent. The use of an easily removable phosphine is also described. Spectroscopic studies indicate that the reaction proceeds via an unusual mechanism which leads to the in situ formation of the salt-free phosphorus ylide, methylenetriphenylphosphorane.
- Lebel, Helene,Paquet, Valerie
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p. 320 - 328
(2007/10/03)
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- Application of palladium-catalyzed Pd-aryl/P-aryl exchanges: Preparation of functionalized aryl phosphines by phosphination of aryl bromides using triarylphosphines
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Palladium-catalyzed Pd-aryl/P-aryl interchange reaction was applied in the synthesis of various functionalized arylphosphines. This phosphination used inexpensive, readily available and air stable triarylphosphines as the phosphinating agents. Broad functional groups were compatible including keto, aldehyde, ester, nitrile, ether, chloride, pyridyl and thiophenyl groups. Halides were found to be good promoter for the rates and yields of the reaction.
- Kwong, Fuk Yee,Lai, Chi Wai,Yu, Michael,Chan, Kin Shing
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p. 5635 - 5645
(2007/10/03)
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- Palladium-catalyzed phosphination of functionalized aryl triflates
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Catalytic user-friendly approach to the syntheses of various functionalized aromatic phosphines from their corresponding substituted aryl triflates and triarylphosphines was accomplished. This method is carried out in neutral media and compatible with man
- Kwong, Fuk Yee,Lai, Chi Wai,Yu, Michael,Tian, Yuan,Chan, Kin Shing
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p. 10295 - 10305
(2007/10/03)
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- Copper-catalyzed synthesis of unsymmetrical triarylphosphines
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Various triarylphosphines have been prepared by coupling diphenylphosphine with aryl iodides with catalytic amounts of CuI in the presence of either K2CO3 or CS2CO3, in good yields. This method can tolerate a variety of functional groups and does not require the use of expensive additives, or harsh reaction conditions, and is palladium free.
- Van Allen, Derek,Venkataraman
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p. 4590 - 4593
(2007/10/03)
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- Copper-catalyzed C-P bond construction via direct coupling of secondary phosphines and phosphites with aryl and vinyl halides
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(Matrix presented) A general method for the coupling of aryl and vinyl halides with diaryl and dialkyl phosphines, as well as with dibutyl phosphite, is reported. This highly efficient transformation is realized through the use of copper(I) iodide as a catalyst, N,N′-dimethylethylenediamine as a ligand, and Cs2CO3 as a base. A variety of sterically hindered and/or functionalized substrates were found to react under these reaction conditions to provide products in good to excellent yields.
- Gelman, Dmitri,Jiang, Lei,Buchwald, Stephen L.
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p. 2315 - 2318
(2007/10/03)
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- Solvent-free palladium-catalyzed phosphination of aryl bromides and triflates with triphenylphosphine
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Palladium-catalyzed phosphination of substituted aryl bromides and triflates using triphenylphosphine as the phosphinating agent was developed using solvent-free conditions. This operationally simple method tolerates ketone, aldehyde, ester, nitrile and e
- Kwong, Fuk Yee,Lai, Chi Wai,Chan, Kin Shing
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p. 3537 - 3539
(2007/10/03)
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- Synthesis of aryl phosphines by phosphination with triphenylphosphine catalyzed by palladium on charcoal
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The palladium-catalyzed phosphination of aryl bromides and triflates by phosphination with triphenylphines to yield aryl phosphines was catalyzed by the thermally stable catalyst palladium on charcoal.
- Lai, Chi Wai,Kwong, Fuk Yee,Wang, Yanchun,Chan, Kin Shing
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p. 4883 - 4885
(2007/10/03)
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- A novel synthesis of functionalised tertiary phosphines by palladium catalysed phosphination with triarylphosphines
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The palladium catalysed Pd-aryl/P-aryl exchange was applied in the synthesis of various functionalised phosphines from their corresponding substituted aryl triflates using triarylphosphines as the phosphinating agents. This method tolerated many functional groups including ketone, aldehyde, ester, nitrile, methyl ether, pyridyl and chloride groups. (C) 2000 Elsevier Science Ltd.
- Kwong, Fuk Yee,Lai, Chi Wai,Tian, Yuan,Chan, Kin Shing
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p. 10285 - 10289
(2007/10/03)
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- A general synthesis of aryl phosphines by palladium catalyzed phosphination of aryl bromides using triarylphosphines
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Palladium catalyzed phosphination of substituted aryl bromides using triarylphosphines as the phosphinating agents has been developed; this method tolerates ketone, aldehyde, ester, nitrile, ether and chloride functional groups.
- Kwong, Fuk Yee,Chan, Kin Shing
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p. 1069 - 1070
(2007/10/03)
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- Allylic substitution in water catalyzed by amphiphilic resin-supported palladium-phosphine complexes
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New amphiphilic resin-supported triarylphosphines PEP (1) were designed and prepared on polyethylene glycol-polystyrene graft copolymer (PEG-PS). Palladium complexes of 1, Pal(PEP)2 (4) and Pd(PEP) (5), catalyzed allylic alkylation of 3-acetoxy-1,3-diphenyl-1-propene (6) and cinnamyl acetate (7) with various nucleophiles including 1,3-dicarbonyl compounds, amino acids, sodium azide, and sodium sulfinate, to give quantitative yields of corresponding allylic substituted products in water.
- Danjo, Hiroshi,Tanaka, Daiki,Hayashi, Tamio,Uozumi, Yasuhiro
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p. 14341 - 14352
(2007/10/03)
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- Preparation and synthetic use of the zerovalent nickel complex by electrochemical reduction
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The generation of Ni(PPh3)4 by electrochemical reduction was carried out in a divided cell containing NiCl2(PPh3)4, PPh3 and n-Bu4NBr in DMF with a lead plate as cathode and a platinum plate as anode under the stream of argon at 60°. Using this Ni(PPh3)4, biphenyls and the heterocyclic compounds were synthesized in fairly good yields.
- Mori, Miwako,Hashimoto, Yasuko,Ban, Yoshio
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p. 631 - 634
(2007/10/02)
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