- 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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- Nickel-catalysed electrochemical coupling between mono- or di-chlorophenylphosphines and aryl or heteroaryl halides
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Nickel-catalysed electrochemical cross-coupling between aryl- or heteroaryl-halides and chlorodiphenylphosphine or dichlorophenylphosphine affords tertiary phosphines in good to high yields.
- Budnikova, Yulia,Kargin, Yuri,Nedelec, Jean-Yves,Perichon, Jacques
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- Photochemical Anion-Promoted Carbon-Sulfur Cleavage Reactions of Diaryl Sulfides, Alkyl Aryl Sulfides, and Related Sulfoxides and Sulfones
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Diaryl sulfides and the related sulfoxides and sulfones react with substances such as diethyl phosphite anion, pinacolone enolate, and diphenylphosphide anion under irradiation to cleave one carbon-sulfur bond and form diethyl arylphosphonates, arylmethyl tert-butyl ketones, and aryldiphenylphosphines.Alkyl aryl sulfides and the related sulfones also experience carbon-sulfur bond cleavage under these conditions to produce arenethiols.Generally, these reactions occur in synthetically useful yields.The reactions of the anions with these sulfides, sulfoxides, and sulfones all require irradiation, but is notable that the reactions of diphenylphosphide anion occur in the visible region of the spectrum.Several lines of evidence suggest that the reaction proceeds via the familiar SRN1 pathway and that the photochemically-induced electron transfer occurs in an arene-anion complex.Thermochemical considerations dictate the cleavage direction in the anion radicals of unsymmetrical sulfides.
- Cheng, Carlos,Stock, Leon M.
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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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- 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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- Nickel-catalyzed C-P cross-coupling by C-CN bond cleavage
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Prosperous coupling: A nickel-catalyzed C-P cross-coupling reaction with Me3SiPPh2 by carbon-cyano bond cleavage has been developed. This method is characterized by its simplicity and wide application to the synthesis of various monophosphorus and P,N bidentate ligands (see scheme).
- Sun, Meng,Zhang, Hong-Yu,Han, Qi,Yang, Kuo,Yang, Shang-Dong
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- Ligand-free palladium catalyzed phosphorylation of aryl iodides
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A reusable ligand-free palladium catalyzed phosphorylation of aryl iodides using PdCl2/tetrabutylammonium bromide is described. Functionalized triarylphosphines were obtained in good to excellent yields in the absence of external reductants and supporting ligands.
- Nowrouzi, Najmeh,Keshtgar, Saba,Bahman Jahromi, Enayatollah
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- Nickel-catalysed P-C bond formation via P-H/C-CN cross coupling reactions
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Nickel-catalysed P-H/C-CN cross coupling reactions take place efficiently under mild reaction conditions affording the corresponding sp2C-P bonds. This transformation provides a convenient method for the preparation of arylphosphines and arylphosphine oxides from the readily available P-H compounds and arylnitriles. This journal is
- Zhang, Ji-Shu,Chen, Tieqiao,Yang, Jia,Han, Li-Biao
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- Efficient potassium hydroxide promoted P-arylation of aryl halides with diphenylphosphine
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A simple synthetic method of triarylphosphine compounds by KOH-promoted P-Arylation reaction of aryl halides with diphenylphosphine is presented. Notably, this transformation could smoothly proceed with high yields under transition-metal-free and mild reaction conditions. In addition, this protocol is valuable for industrial application due to the convenient operation and readily accessible aromatic halides. A possible explanation of the reaction mechanism was proposed based on the experimental data.
- Chen, Jin,Dai, Bencai,Liu, Changchun,Shen, Zhihao,Zhou, Yang
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- ARYLATION CATALYTIQUE D'ORGANOPHOSPHORES. PRODUITS DE L'ARYLATION, CATALYSEE PAR LES SELS DE NICKEL (II), DE COMPOSES DU PHOSPHORE TRICOORDINE
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Analysis of the products from the nickel (II) bromide catalysed arylation of tricoordinated phosphorus compounds R2P-Z (Z = H, Cl, SR,NR2) pointed out that this arylation always takes place on phosphorus resulting at first in formation of pseudophosphonium salts.Only the aminophosphonium salts are stable under reaction conditions; the other salts undergo several transformations which can be brought together in a general reactivity scheme to account for all the side products.On regard to other heteroatoms these results point out a particular ability of phosphorus to be arylated under nickel (II) catalysis.The reaction with secondary phosphines can be applied to synthetise diarylphosphonium salts.
- Cristau, Henri-Jean,Chene, Alain,Christol, Henri
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- Palladium-Catalyzed C-P(III) Bond Formation by Coupling ArBr/ArOTf with Acylphosphines
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Palladium-catalyzed C-P bond formation reaction of ArBr/ArOTf using acylphosphines as differential phosphination reagents is reported. The acylphosphines show practicable reactivity with ArBr and ArOTf as the phosphination reagents, though they are inert to the air and moisture. The reaction affords trivalent phosphines directly in good yields with a broad substrate scope and functional group tolerance. This reaction discloses the acylphosphines' capability as new phosphorus sources for the direct synthesis of trivalent phosphines.
- Chen, Xingyu,Wu, Hongyu,Yu, Rongrong,Zhu, Hong,Wang, Zhiqian
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p. 8987 - 8996
(2021/06/30)
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- Diverse C-P Cross-Couplings of Arylsulfonium Salts with Diarylphosphines via Selective C-S Bond Cleavage
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Diverse C-P cross-couplings of arylthianthrenium salts with diarylphosphines producing various triarylphosphines via highly selective C-S bond cleavage are reported. In the absence of catalyst, the reaction of arylthianthrenium salts with diarylphosphines undergoes phosphinative ring opening exclusively via the cleavage of an endocyclic C-S bond of a thianthrene skeleton. The use of a palladacycle catalyst under otherwise the same conditions enables the phosphination via the cleavage of an exocyclic C-S bond with significantly higher speed.
- Ye, Yun,Zhu, Jie,Huang, Yinhua
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supporting information
p. 2386 - 2391
(2021/04/05)
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- 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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- Preparing method of triarylphosphine compound
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The invention belongs to the technical field of medicine and natural compound chemical intermediates and relevant chemistry, and provides a preparing method of a triarylphosphine compound. According to the preparing method, a diphenylphosphine compound and aryl halide serve as raw materials, participation of transition metal catalysts is not needed, and the triarylphosphine compound is constructedin one step under the heating condition. The preparing method has the advantages that according to the reaction, the metal or non-metal catalysts are not needed for catalytic reactions, the triarylphosphine compound is clean and free of pollution, the reaction condition is mild, the operation and aftertreatment are simple, and the substrate compatibility is good.
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Paragraph 0036; 0037-0039
(2019/07/16)
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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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- Metal-Free Reduction of Phosphine Oxides, Sulfoxides, and N-Oxides with Hydrosilanes using a Borinic Acid Precatalyst
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The general reduction of phosphine oxides, sulfoxides, and amine N-oxides was achieved by combining bis(2-chlorophenyl)borinic acid with phenylsilane. The reaction was shown to tolerate a wide range of substrates and could be performed under mild conditions, with only 2.5 mol % of the easily synthesized catalyst. Mechanistic investigations pointed to a key borohydride as the real catalyst and at bis(2-chlorophenyl)borinic acid as a precatalyst.
- Chardon, Aurélien,Maubert, Orianne,Rouden, Jacques,Blanchet, Jér?me
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p. 4460 - 4464
(2017/11/22)
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- Method for synthesizing phosphorus-containing organic matter
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The invention provides a method for synthesizing a phosphorus-containing organic matter; the method comprises: under the protection of an inert gas, subjecting halohydrocarbon or sulfonate shown in formula 1 and an acylphosphine compound shown in formula 2 to coupling reaction in the presence of a transition metal catalyst, a solvent and an additive to obtain a trivalent phosphine compound shown in formula 3, described in the description, wherein each of R1, R2 and R3 is independently at least one of C1-C16 alkyl, C6-C20 aryl and C4-C15 heterocyclic aryl; the additive is an inorganic base or organic base; in the method, the acylphosphine compound is used as a safety phosphine reagent used for performing transition metal catalyzed carbon-phosphorus bond coupling reaction so as to synthesize the phosphorus-containing organic matter; the method has high yield and good safety and convenience.
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Paragraph 0032-0035
(2017/08/31)
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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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p. 3404 - 3406
(2016/07/11)
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- Convenient Formation of Triarylphosphines by Nickel-Catalyzed C-P Cross-Coupling with Aryl Chlorides
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A convenient strategy has been developed for the preparation of various phosphine ligands in good to excellent yields through a nickel-catalyzed C-P bond-forming step. This reaction proceeded smoothly and tolerated a variety of functional groups to provide a new method for the synthesis of important phosphine ligands through the direct cleavage of a C-Cl bond. A convenient strategy has been developed for the preparation of various phosphine ligands in good to excellent yields through a nickel-catalyzed C-P bond-forming step. This reaction proceeded smoothly and tolerated a variety of functional groups to provide a new method for the synthesis of important phosphine ligands through the direct cleavage of a C-Cl bond.
- Sun, Meng,Zang, Yu-Shi,Hou, Le-Kai,Chen, Xiang-Xiang,Sun, Wei,Yang, Shang-Dong
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supporting information
p. 6796 - 6801
(2016/02/18)
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- Novel preparation of ion-supported triphenylphosphines and their synthetic utility
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Novel ion-supported Ph3P compounds, 4-(diphenylphosphino)- benzyltrimethylammonium bromide (A) and N-methyl-N-[4-(diphenylphosphino) -benzyl]pyrrolidinium bromide (B), were prepared. Because of their stability in air, ion-supported Ph3P A and B could be used for the halogenation of alcohols, the esterification of carboxylic acid with the Mitsunobu reaction, the Mizoroki-Heck reaction, and the Sonogashira reaction. The advantages of using these ion-supported Ph3P A and B are the simple isolation of the products by ether extraction due to their poor solubility in ether, and the easy recovery of the co-product, ion-supported Ph3PO, by filtration in high yields (>90%), which could be regenerated and reused for the same reactions, in the halogenation of alcohols and the esterification of carboxylic acid with the Mitsunobu reaction. On the other hand, ionic liquid reaction media containing Pd(OAc)2 or PdCl2 and ion-supported Ph3P A or B as catalysts could be reused for the same Mizoroki-Heck reaction and the Sonogashira reaction maintaining high yields, using iodotoluene with methyl acrylate and phenylacetylene, respectively.
- Imura, Yumi,Shimojuh, Naoya,Kawano, Yuhta,Togo, Hideo
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scheme or table
p. 3421 - 3426
(2010/06/19)
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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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- Preparation of diphenyl phosphide and substituted phosphines using alkali metal in silica gel (M-SG)
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Alkali metals absorbed in silica gel (the M-SG reagents) efficiently cleave C-P bonds in triaryl- and diarylphosphines. The resulting alkali metal phosphides can serve as useful building blocks for a variety of phosphines. Alkyldiarylphosphines undergo exclusive aryl group cleavage.
- Nandi, Partha,Dye, James L.,Bentley, Philip,Jackson, James E.
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supporting information; experimental part
p. 1688 - 1692
(2009/09/06)
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- (p-tolyl)dichlorophosphine and di(p-tolyl)chlorophosphine sources of new organophosphorus(III) and (V) compounds
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The purpose of our present work was to study some chemical properties of p-tolyldichlorophosphine and di(p-tolyl)chlorophosphine involved in reactions with organo-lithium compounds, with 1,2-diols and also when are reactants in variants of Reformatsky and Mannich reactions, in order to obtain some new substances of trivalent and pentavalent phosphorus useful for our further investigations. All the new phosphorus(III) and (V) compounds were obtained in fair yields, and were characterized by elemental analysis, IR, and NMR spectroscopy. They will find potential synthetic utility as convenient ligands for transition metals and reagents for the preparation of phosphonium salts, for obtaining chiral substances and as biologically active ring substances.
- Fǎgǎdar-Cosma, Eugenia,Fǎgǎdar-Cosma, Gheorghe
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p. 211 - 217
(2007/10/03)
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- Catalysis using phosphine oxide and sulfoxide compounds
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Phosphine oxide and sulfoxide compounds were used with transition metals, preferably palladium and nickel, to produce biaryls, arylthiols, arylphosphine oxides and arylamines via cross-coupling reactions with aryl halides and arylboronic acids, aryl Grignard reagents, thiols, phosphine oxides or amines.
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- Electrosynthesis of triorganylphosphines from organic halides and chlorophosphines, catalyzed by nickel complexes
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The possibility of cross coupling of organic halides and chlorophosphines under the action of electrochemically generated Ni(0) complexes of 2,2′-bipy is shown. The final triorganylphosphines are formed by several pathways, including reaction of the σ complex of ArNiX with chlorophosphine and electron transfer-induced reductive elimination of Ph2PArNiX, leading to the cross-coupling product.
- Budnikova,Kargin,Sinyashin
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p. 524 - 528
(2007/10/03)
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- Water soluble phosphines VIII. Palladium-catalyzed P-C cross coupling reactions between primary or secondary phosphines and functional aryliodides - A novel synthetic route to water soluble phosphines
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Tertiary phosphines Ph2P-Ar and PhP(Ar)2 containing mono-and disubstituted aromatic ring systems Ar (Ar = C6H4-X and C6H3-XY; X, Y = Me, OH, NH2, COOH, COOMe and SO3Na) are accessible in good yields by Pd(0)-catalyzed cross coupling reactions between diphenylphosphine or phenylphosphine and substituted aryliodides I-C6H4-X or I-C6H3-XY in organic solvents (dimethylacetamide, acetonitrile, methanol) using organic amines or potassium and sodium acetate as bases. If the primary phosphine is employed in the appropriate stoichiometric ratio, functionalized secondary phosphines, e.g. Ph(H)P-C6H4-p-SO3Na, may be obtained selectively.
- Herd, Oliver,Hessler, Antonella,Hingst, Martin,Tepper, Michael,Stelzer, Othmar
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- Palladium-Catalyzed Coupling of Aryl Halides with (Trimethylstannyl)diphenylphosphine and (Trimethylsilyl)diphenylphosphine
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The palladium-catalyzed reaction of aryl halides with either (trimethylsilyl)diphenylphosphine or (trimethylstannyl)diphenylphosphine gives aryldiphenylphosphines in good yields, under relatively mild conditions (50-70 deg C, benzene).The reaction tolerates a number of functional groups including methyl ethers, esters, ketones, nitriles, anilides, and certain halogens.The nitro and aldehyde groups as well as compounds containing groups such as amino and hydroxyl are not tolerated.
- Tunney, S. E.,Stille, J. K.
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p. 748 - 753
(2007/10/02)
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- Carbon Acidity. 63. Equilibrium Ion Pair Acidities of Some Phosphorus-Substituted Carbon Acids
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Ion-pair C-H acidities are reported as pKCsCHA for bis(diphenylphosphino)methane (1, 31.1), (p-phenylbenzyl)diphenylphosphine (3, 31.0), p-tolyldiphenylphosphine (4, 37.9), and several of the corresponding phosphine oxides.The diphenylphosphine group is about as anion stabilizing as p-biphenyl.The Ph2P(O) group is additionally stabilizing because of enhanced ion-pair interaction.The pKCsCHA of benzyldiphenylphosphine (2) can be estimated to be about 32.
- Streitwieser, Andrew,Juaristi, Eusebio
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p. 768 - 770
(2007/10/02)
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