- Palladium anchored on a covalent organic framework as a heterogeneous catalyst for phosphorylation of aryl bromides
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A simple azine-linked covalent organic framework (COF) with high thermal and chemical stabilities has been prepared by using deep eutectic solvent (DES) as green media. The as-synthesized COF was employed as heterogeneous ligand for immobilization of PdII. The obtained Pd-supported COF nanoparticles catalyst (defined as Pd/TFPT-Azine-COF) was found to be an efficient heterogeneous catalyst for the Hirao reaction of aryl halides and dialkyl phosphites or diphenylphosphine oxide with excellent recyclability, reusability, and retention of crystallinity.
- Chen, Yu-Xuan,Zhang, Shuo,Xue, Yu-Jie,Mo, Li-Ping,Zhang, Zhan-Hui
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- Method for synthesizing trisubstituted arylphosphine oxide species by using diphenyl(tert-butyl)phosphine as substrate
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The invention relates to a method for synthesizing a trisubstituted arylphosphine oxide species by taking diphenyl(tert-butyl)phosphine as a substrate, belonging to the technical field of organic phosphine synthesis. The method comprises the following steps: with a transition metal palladium salt as a catalyst and a hydrazine compound and diphenyl(tert-butyl)phosphine as reaction substrates, adding the reaction substrates and an alkali compound into a reaction solvent, carrying out stirring and heating, conducting reacting for a certain period of time to obtain a reaction solution, and separating and purifying the reaction solution to obtain a trisubstituted arylphosphine oxide compound, wherein the hydrazine compound is any one selected from aromatic hydrazine and aromatic heterocyclic hydrazine; and the transition metal palladium salt catalyst is selected from any one of Pd(OAc)2, Pd(dba)2 and PdCl2. Compared with a traditional synthesis method, the method has the advantages that the use of diarylphosphine oxide hydrogen is avoided, raw materials are easy to obtain, reaction conditions are mild, yield is high, and reaction selectivity is good. In general, the method is friendly to environment and simple in synthesis process, and has certain industrial application prospects.
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Paragraph 0019-0020; 0021-0023
(2021/07/28)
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- Palladium-Catalyzed C-P Bond-Forming Reactions of Aryl Nonaflates Accelerated by Iodide
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An iodide-accelerated, palladium-catalyzed C-P bond-forming reaction of aryl nonaflates is described. The protocol was optimized for the synthesis of aryl phosphine oxides and was found to be tolerant of a wide range of aryl nonaflates. The general nature of this transformation was established with coupling to other P(O)H compounds for the synthesis of aryl phosphonates and an aryl phosphinate. The straightforward synthesis of stable, isolable aryl nonaflates, in combination with the rapid C-P bond-forming reaction allows facile preparation of aryl phosphorus target compounds from readily available phenol starting materials. The synthetic utility of this general strategy was demonstrated with the efficient preparation of an organic light-emitting diode (OLED) material and a phosphonophenylalanine mimic.
- McErlain, Holly,Riley, Leanne M.,Sutherland, Andrew
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p. 17036 - 17049
(2021/11/18)
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- Preparation method of aromatic phosphine oxide compound
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The invention relates to the field of organic synthesis, in particular to a preparation method of an aromatic phosphine oxide compound. The preparation method comprises the following steps: adding a P(O)-H compound, a fluoroaromatic compound and an alkali reagent into an organic solvent, conducting mixing, performing stirring for reaction, and carrying out cooling to obtain a mixed solution; and carrying out washing and extracting to obtain an organic phase, drying and distilling the organic phase, and performing column chromatography to obtain the aromatic phosphine oxide compound. The method is simple in reaction operation, only a proper amount of alkali needs to be added, special reaction conditions such as ligands, catalysts and additives are not needed, the reaction is simple and efficient, and good industrial application prospects are achieved.
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Paragraph 0052-0054
(2021/10/20)
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- NiCl 2as a Cheap and Efficient Precatalyst for the Coupling of Aryl Fluorosulfonate and Phosphite/Phosphine Oxide
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Herein, NiCl 2is employed as a cheap precatalyst in the formation of C(sp 2)-P bond via cross-coupling reaction of phenol derivatives and phosphine oxides/phosphites. This catalytic system allows a variety of phenols with diverse functional groups to transform into phosphates with good yields. No additional additive is used in this reaction.
- Yan, Wenjie,Zhou, Hongbo,Li, Haoyuan,Hu, Huimin,Yu, Ying,Guo, Shengmei,Cai, Hu
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p. 1453 - 1456
(2021/07/20)
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- Visible-Light-Induced Nickel-Catalyzed P(O)-C(sp2) Coupling Using Thioxanthen-9-one as a Photoredox Catalysis
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An efficient method has been developed for photocatalytic P(O)-C(sp2) coupling of (hetero)aryl halides with H-phosphine oxides or H-phosphites under the irradiation of visible light or sunlight. The thioxanthen-9-one/nickel dual catalysis mediates this ph
- Zhu, Da-Liang,Jiang, Shan,Wu, Qi,Wang, Hao,Chai, Lu-Lu,Li, Hai-Yan,Li, Hong-Xi
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supporting information
p. 160 - 165
(2021/01/09)
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- Cu/Picolinamides-Catalyzed Coupling of (Hetero)aryl Halides with Secondary Phosphine Oxides and Phosphite?
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Some 4-hydroxy-picolinic acid derived amides were revealed as more efficient ligands for Cu-catalyzed coupling of (hetero)aryl halides with secondary phosphine oxides and phosphites. Only 3—5 mol% CuI and ligands were required to ensure coupling with a number of (hetero)aryl bromides and iodides to complete at 120 oC in 10—20 h.
- Fang, Chao,Wei, Bangguo,Ma, Dawei
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supporting information
p. 2957 - 2961
(2021/08/23)
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- Selective C-P(O) Bond Cleavage of Organophosphine Oxides by Sodium
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Sodium exhibits better efficacy and selectivity than Li and K for converting Ph3P(O) to Ph2P(OM). The destiny of PhNa co-generated is disclosed. A series of alkyl halides R4X and aryl halides ArX all react with Ph2P(ONa) to produce the corresponding phosphine oxides in good to excellent yields.
- Zhang, Jian-Qiu,Ikawa, Eiichi,Fujino, Hiroyoshi,Naganawa, Yuki,Nakajima, Yumiko,Han, Li-Biao
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p. 14166 - 14173
(2020/11/13)
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- Practical C–P bond formation via heterogeneous photoredox and nickel synergetic catalysis
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An efficient C–P bond formation reaction was developed by virtue of the synergetic catalysis strategy by merging heterogeneous photocatalysis and nickel catalysis. This platform utilizing cadmium sulfide semiconductors as heterogeneous photocatalysts and
- Koranteng, Ernest,Liu, Yi-Yin,Liu, Si-Yue,Wu, Qiang-Xian,Lu, Liang-Qiu,Xiao, Wen-Jing
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p. 1841 - 1846
(2019/11/11)
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- Decarbonylative C-P bond formation using aromatic esters and organophosphorus compounds
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Ni-catalyzed C-P bond formation was achieved using aromatic esters as unconventional aryl sources. The key to success was the use of a thiophene-based diphosphine ligand (dcypt). Several aromatic esters including heteroaromatics can be coupled with phosphine oxides and phosphates, providing aryl phosphorus compounds. The synthetic utility of the method was demonstrated by application of the present protocol to the sequential coupling reactions.
- Isshiki, Ryota,Muto, Kei,Yamaguchi, Junichiro
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supporting information
p. 1150 - 1153
(2018/02/23)
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- Efficient nickel-catalyzed phosphinylation of C-S bonds forming C-P bonds
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The first nickel-catalyzed phosphinylation of C-S bonds forming C-P bonds is developed. This transformation can proceed readily with the simple Ni(cod)2 at a loading down to 0.1 mol% at the 10 mmol scale. A variety of aryl sulfur compounds, i.e. sulfides, sulfoxides and sulfones all couple with P(O)-H compounds to produce the corresponding organophosphorus compounds in high yields, which provides an efficient new method for the construction of C-P bonds.
- Yang, Jia,Xiao, Jing,Chen, Tieqiao,Yin, Shuang-Feng,Han, Li-Biao
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supporting information
p. 12233 - 12236
(2016/10/21)
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- Nickel-catalyzed phosphorylation of aryl triflates with P([Formula presented] compounds
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A nickel-catalyzed phosphorylation of aryl triflates with P([Formula presented] compounds is disclosed. This reaction can proceed smoothly under a mild reaction condition, producing the corresponding aryl phosphorus compounds in good to high yields.
- Yang, Jia,Xiao, Jing,Chen, Tieqiao,Han, Li-Biao
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p. 120 - 124
(2016/08/23)
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- Cobalt catalysed, copper assisted C(sp2)-P cross coupling
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An efficient protocol for the cross coupling of styrenyl/aryl halides and H-phosphinate has been developed using a unique Co/Cu catalytic system in the absence of any additional ligand for the first time. A library of diversely functionalised styrenyl/ary
- Ghosh, Tubai,Maity, Pintu,Kundu, Debasish,Ranu, Brindaban C.
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p. 9556 - 9564
(2016/11/11)
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- A cyclodiphosphazane based pincer ligand, [2,6-{μ-(tBuN)2P(tBuHN)PO}2C6H3I]: NiII, PdII, PtII and CuI complexes and catalytic studies
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Synthesis and late-transition metal complexes of pincer capable cyclodiphosphazane, 2,6-{μ-(tBuN)2P(tBuHN)PO}2C6H3I (1) are described. The condensation of 2-iodoresorcinol with cis-{ClP(μ-NtBu)2PN(H)tBu} produced a difunctional derivative 1 in good yield. The treatment of Ni(COD)2, Pd2(dba)3·CHCl3 or Pt(PPh3)4 with 1 afforded pincer complexes [2,6-{μ-(tBuN)2P(tBuHN)PO}2C6H3MI] (2 M = Ni; 3 M = Pd and 4 M = Pt). The reaction of complex 3 with copper halides resulted in the formation of heterobimetallic complexes bridged by rhombic {Cu(μ-X)}2 units, [{{Cu(μ-X)}2}{μ-(tBuN)2P(tBuHN)PO}2C6H3PdI] (5 X = I and 6 X = Br). The crystal structures of 1-3, 5 and 6 were established by single X-ray diffraction studies. The palladium complex 3 was tested for catalytic P-arylation of diphenylphosphine oxide (Ph2P(O)H) under microwave irradiation. Moderate to good catalytic activity was observed with aryl bromides. This journal is
- Ananthnag, Guddekoppa S.,Mague, Joel T.,Balakrishna, Maravanji S.
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p. 3785 - 3793
(2015/03/04)
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- Palladium-catalyzed air-based oxidative coupling of arylboronic acids with H-phosphine oxides leading to aryl phosphine oxides
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We present a novel and highly efficient methodology that allows for the construction of C-P bonds via the palladium-catalyzed air-based oxidative coupling of various commercially available arylboronic acids with easily oxidized H-phosphine oxides leading to valuable aryl phosphine oxides, particularly triarylphosphine oxides, with the use of air as the green oxidant, broad substrate applicability and good to excellent yields. The described catalytic system should be an efficient complement to the Chan-Lam type reaction and be useful in synthetic programs. This journal is the Partner Organisations 2014.
- Fu, Tingting,Qiao, Hongwei,Peng, Zhimin,Hu, Gaobo,Wu, Xueji,Gao, Yuxing,Zhao, Yufen
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p. 2895 - 2902
(2014/05/06)
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- A copper-catalyzed variant of the Michaelis-Arbuzov reaction
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As part of our studies on copper-catalyzed arylation of nucleophiles, we report on Michaelis-Arbuzov reactions with a novel catalytic system, featuring a copper(I) salt as precatalyst without any additional ligand. This procedure is an interesting alternative to the use of expensive and toxic transition metals (nickel, palladium) traditionally used as catalysts in Michaelis-Arbuzov reactions. Our approach allows the synthesis from triethylphosphite, diethyl aryl phosphonite, and diaryl ethylphosphinite of various aryl phosphonates, aryl phosphinates, and aryl phosphine oxides, respectively. These families of compounds are essential owing to their respective importance in bioorganic and medical chemistry, their applicability as flame retardants, and their usability in coordination chemistry and catalysis. Copper load of this! The first copper-catalyzed Michaelis-Arbuzov reactions are described. The methodology is ligand-free and allows the direct synthesis of various aryl phosphonates, aryl phosphinates, and aryl phosphine oxides from aryl iodides.
- Ballester, Jorge,Gatignol, Jeremie,Schmidt, Guntram,Alayrac, Carole,Gaumont, Annie-Claude,Taillefer, Marc
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p. 1549 - 1552
(2014/06/24)
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- Phosphorus-carbon bond formation: Palladium-catalyzed cross-coupling of H-phosphinates and other P(O)H-containing compounds
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Two generally applicable systems have been developed for the cross-coupling of P(O)H compounds with Csp2-X and related partners. Palladium catalysis using a ligand/additive combination, typically either xantphos/ethylene glycol or 1,1-bis(diphenylphosphino)ferrocene/1,2- dimethoxyethane, with diisopropylethylamine as the base, proved to be generally useful for the synthesis of numerous P-C containing compounds. Routinely, 2 mol% of catalyst are employed (less than half the amount typically employed in most other literature reports). In most cases, excellent results are obtained with a variety of electrophiles (RX, where R=alkenyl, allyl, alkynyl, etc.). The full account of our studies is disclosed, including tandem hydrophosphinylation/ coupling and coupling/coupling for doubly catalytic phosphorus-carbon bond formation. The methodology compares favorably with any existing literature report. The use of an additive appears to be a generally useful strategy to control the reactivity of phosphinylidene compounds. Copyright
- Berger, Olivier,Petit, Christelle,Deal, Eric L.,Montchamp, Jean-Luc
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supporting information
p. 1361 - 1373
(2013/06/26)
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- [NiCl2(dppp)]-catalyzed cross-coupling of aryl halides with dialkyl phosphite, diphenylphosphine oxide, and diphenylphosphine
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We present a general approach to C-P bond formation through the cross-coupling of aryl halides with a dialkyl phosphite, diphenylphosphine oxide, and diphenylphosphane by using [NiCl2(dppp)] as catalyst (dppp=1,3-bis(diphenylphosphino)propane). This catalyst system displays a broad applicability that is capable of catalyzing the cross-coupling of aryl bromides, particularly a range of unreactive aryl chlorides, with various types of phosphorus substrates, such as a dialkyl phosphite, diphenylphosphine oxide, and diphenylphosphane. Consequently, the synthesis of valuable phosphonates, phosphine oxides, and phosphanes can be achieved with one catalyst system. Moreover, the reaction proceeds not only at a much lower temperature (100-120 °C) relative to the classic Arbuzov reaction (ca. 160-220 °C), but also without the need of external reductants and supporting ligands. In addition, owing to the relatively mild reaction conditions, a range of labile groups, such as ether, ester, ketone, and cyano groups, are tolerated. Finally, a brief mechanistic study revealed that by using [NiCl2(dppp)] as a catalyst, the NiII center could be readily reduced in situ to Ni0 by the phosphorus substrates due to the influence of the dppp ligand, thereby facilitating the oxidative addition of aryl halides to a Ni0 center. This step is the key to bringing the reaction into the catalytic cycle. Making bonds: C-P bonds were formed by the Ni-catalyzed cross-coupling of aryl halides and phosphorus substrates without the need of external reductants. Aryl bromides and less reactive aryl chlorides underwent smooth coupling with several different phosphorus substrates to afford phosphonates, phosphine oxides, and phosphines (see scheme; dppp=1,3-bis(diphenylphosphino)propane). Due to the mild reaction conditions, a range of labile groups, such as ether, ester, ketone, and cyano groups, are tolerated. Copyright
- Zhao, Yu-Long,Wu, Guo-Jie,Li, You,Gao, Lian-Xun,Han, Fu-She
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supporting information; experimental part
p. 9622 - 9627
(2012/09/07)
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- Nickel-catalyzed C-P cross-coupling of diphenylphosphine oxide with aryl chlorides
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A novel protocol for the preparation of various diarylphosphine oxide compounds via a Ni-catalyzed cross-coupling of aryl chlorides with R 2P(O)H has been developed. Notably, this process exhibits the following very attractive features: (i) the process is simpler and operates under mild reaction conditions; (ii) the process is generally cheaper in part because the more accessible aryl chloride is used to form the C-P bond; (iii) the process avoids the need for simultaneous preparation and use of Ar 2P(O)M. The Royal Society of Chemistry 2012.
- Zhang, Hong-Yu,Sun, Meng,Ma, Yan-Na,Tian, Qiu-Ping,Yang, Shang-Dong
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p. 9627 - 9633
(2013/01/16)
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- Homolytic substitution at phosphorus for the synthesis of alkyl and aryl phosphanes
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(Chemical Equation Presented) A transition-metal-free radical phosphonation using Me3SnPPh2 and the less toxic Me 3SiPPh2 is reported. These readily available reagents react highly efficiently with primary and secondary alkyl radicals. Moreover, aryl radicals and tertiary alkyl radicals are phosphonated with Me 3SnPPh2 (see scheme; R = aryl, alkyl, vinyl; X = 1, Br, OC(S)imidazolyl). DFT calculations provide insights into the mechanism of the reaction.
- Vaillard, Santiago E.,Mueck-Lichtenfeld, Christian,Grimme, Stefan,Studer, Armido
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p. 6533 - 6536
(2008/09/17)
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