- Synthesis of arylphosphonates by arylation of phosphite anions using diaryliodonium salts
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An efficient synthesis of arylphosphonates 3 is described. The method involves simple stirring of the dialkyl phosphite salts 2 with diaryliodonium salts 1 in dimethylformamide.
- Liu,Chen
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- 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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- Microwave assisted P–C coupling reactions without directly added P-ligands
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Our group introduced a green protocol for the Pd(OAc)2- or NiCl2-catalyzed P–C coupling reaction of aryl halides and various > P(O)H-compounds under MW conditions without directly added P-ligands. The reactivity of a few aryl derivatives in the Pd(OAc)2-catalyzed Hirao reaction was also studied. An induction period was observed in the reaction of bromobenzene and diphenylphosphine oxide. Finally, the less known copper(I)-promoted P–C coupling reactions were investigated experimentally. The mechanism was explored by quantum chemical calculations.
- Henyecz, Réka,Huszár, Bianka,Keglevich, Gy?rgy,Mucsi, Zoltán
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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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- Photoinduced transition-metal and external photosensitizer free cross-coupling of aryl triflates with trialkyl phosphites
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Photoinduced phosphonation of aryl triflates with trialkyl phosphites via a tandem single-electron-transfer, C-O bond cleavage and Arbuzov rearrangement process in the absence of transition-metal and external photosensitizer is reported herein. The protoc
- Dou, Qian,Geng, Li,Cheng, Bin,Li, Chao-Jun,Zeng, Huiying
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supporting information
p. 8429 - 8432
(2021/09/02)
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- Visible-light-mediated phosphonylation reaction: formation of phosphonates from alkyl/arylhydrazines and trialkylphosphites using zinc phthalocyanine
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In this work, we developed a ligand- and base-free visible-light-mediated protocol for the photoredox syntheses of arylphosphonates and, for the first time, alkyl phosphonates. Zinc phthalocyanine-photocatalyzed Csp2-P and Csp3-P bond formations were efficiently achieved by reacting aryl/alkylhydrazines with trialkylphosphites in the presence of air serving as an abundant oxidant. The reaction conditions tolerated a wide variety of functional groups.
- Hosseini-Sarvari, Mona,Koohgard, Mehdi
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p. 5905 - 5911
(2021/07/12)
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- Palladium-catalyzed one-pot phosphorylation of phenols mediated by sulfuryl fluoride
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We report a general palladium-catalyzed one-pot procedure for the synthesis of phosphonates, phosphinates and phosphine oxides from phenols mediated by sulfuryl fluoride. It features mild conditions, broad substrate scope, high functionality tolerance and water insensitivity. The utility of this procedure has been well demonstrated by gram-scale synthesis, sequential synthesis of click chemistry building blocks, late-stage decoration of drugs and natural products and on-DNA synthesis of phosphine oxide for a DNA-encoded library (DEL).
- Zhang, Yiyuan,Chen, Wanting,Tan, Tingting,Gu, Yuang,Zhang, Shuning,Li, Jie,Wang, Yan,Hou, Wei,Yang, Guang,Ma, Peixiang,Xu, Hongtao
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supporting information
p. 4588 - 4591
(2021/05/17)
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- Fe-MIL-101 modified by isatin-Schiff-base-Co: a heterogeneous catalyst for C-C, C-O, C-N, and C-P cross coupling reactions
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A metal-organic framework functionalized with a cobalt-complex is preparedviapost-synthetic modification of Fe-MIL-101-NH2. Initially, Fe-MIL-101-NH2reacted with isatin to produce Fe-MIL-101-isatin-Schiff-base, which can anchor the cobalt by the addition of cobalt acetate. The resulting MOF-Co catalyst is characterized by employing multiple techniques. This new modified MOF acts as a heterogeneous and recyclable catalyst for efficient Ullmann, Buchwald-Hartwig, Hirao, Hiyama and Mizoroki-Heck cross-coupling reactions of several aryl halides/phenylboronic acid/phenyltosylate with phenols, anilines/heterocyclic amines, triethyl phosphite, triethoxyphenylsilane and alkenes and generates the expected coupling products in good to high yields.
- Farrokhi, Alireza,Rouzifar, Majid,Sansano, José Miguel,Sobhani, Sara
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p. 19963 - 19976
(2021/11/12)
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- Non-innocent Radical Ion Intermediates in Photoredox Catalysis: Parallel Reduction Modes Enable Coupling of Diverse Aryl Chlorides
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We describe a photocatalytic system that elicits potent photoreductant activity from conventional photocatalysts by leveraging radical anion intermediates generated in situ. The combination of an isophthalonitrile photocatalyst and sodium formate promotes diverse aryl radical coupling reactions from abundant but difficult to reduce aryl chloride substrates. Mechanistic studies reveal two parallel pathways for substrate reduction both enabled by a key terminal reductant byproduct, carbon dioxide radical anion.
- Chernowsky, Colleen P.,Chmiel, Alyah F.,Wickens, Zachary K.,Williams, Oliver P.,Yeung, Charles S.
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supporting information
p. 10882 - 10889
(2021/07/31)
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- A hydrophilic heterogeneous cobalt catalyst for fluoride-free Hiyama, Suzuki, Heck and Hirao cross-coupling reactions in water
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A hydrophilic heterogeneous cobalt catalyst of chitosan, denoted as mTEG-CS-Co-Schiff-base, has been successfully prepared. This newly synthesized catalyst was characterized by different methods such as XRD, FE-SEM, TEM, TGA, FT-IR, 13C{1H} CP/MAS NMR, XPS and ICP analyses. The catalyst displayed excellent activity for the palladium and fluoride-free Hiyama, Suzuki, Heck and Hirao reactions of various aryl iodides, bromides and chlorides (i.e., the most challenging aryl halides which are cheaper and more widely available than aryl iodides and bromides) in water. The presence of triethylene glycol tags with hydrophilic character on the Co-complex supported on chitosan provides dispersion of the catalyst particles in water, which leads to higher catalytic performance and also facile catalyst recovery by successive extraction. It was reused for at least six successive runs without any discernible decrease in its catalytic activity or any remarkable changes in catalyst structure. The use of water as a green solvent, without requiring any additive or organic solvent, as well as use of a low cost and abundant cobalt catalyst instead of expensive Pd catalysts along with the catalyst recovery and scalability, make this method favorable from environmental and economic points of view for the C-C and C(sp2)-P coupling reactions. Notably, this is the first report on the application of a cobalt catalyst in Hiyama reactions.
- Sobhani, Sara,Hosseini Moghadam, Hadis,Skibsted, J?rgen,Sansano, José Miguel
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p. 1353 - 1365
(2020/03/11)
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- Catalyst-free phosphorylation of aryl halides with trialkyl phosphites through electrochemical reduction
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A catalyst-free electrochemical cross-coupling reaction of aryl halides with trialkyl phosphite has been developed. This reaction proceeds in an undivided cell with a low-cost Ni anode and a graphite cathode under mild and neutral conditions. A wide range of functional groups are well-tolerated and the phosphorylated product can be obtained on the gram scale, showing that this transformation has the potential to be a valuable method for the construction of aromatic carbon-phosphorus bonds.
- Wang, Shuai,Yang, Cheng,Sun, Shuo,Wang, Jianbo
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supporting information
p. 14035 - 14038
(2019/11/25)
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- C-P bond construction catalyzed by NiII immobilized on aminated Fe3O4@TiO2 yolk-shell NPs functionalized by (3-glycidyloxypropyl)trimethoxysilane (Fe3O4@TiO2 YS-GLYMO-UNNiII
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NiII immobilized on aminated Fe3O4@TiO2 yolk-shell NPs functionalized by (3-glycidyloxypropyl)trimethoxysilane (Fe3O4@TiO2 YS-GLYMO-UNNiII) was prepared as a stable, h
- Ghasemzadeh, Maryam Sadat,Akhlaghinia, Batool
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p. 5341 - 5356
(2019/04/05)
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- Nickel-Catalyzed Electrochemical Phosphorylation of Aryl Bromides
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A nickel-catalyzed electrochemical cross-coupling reaction of aryl bromides with dialkyl phosphites, ethyl phenylphosphinate, and diphenylphosphine oxide has been developed. This reaction utilizes a simple undivided cell with inexpensive carbon electrodes to synthesize aryl phosphonates, aryl phosphinates, and arylphosphine oxides at room temperature. This protocol provides a mild and efficient route for the construction of C-P bond in moderate to high yields with broad substrate scope.
- Bai, Ya,Liu, Nian,Wang, Shutao,Wang, Siyu,Ning, Shulin,Shi, Lingling,Cui, Lili,Zhang, Zhuoqi,Xiang, Jinbao
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supporting information
p. 6835 - 6838
(2019/09/30)
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- Visible-Light-Mediated Metal-Free Synthesis of Aryl Phosphonates: Synthetic and Mechanistic Investigations
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This work describes a straightforward access to a large variety of aryl phosphonates by the simple combination of diaryliodonium salts with phosphites in the presence of a base and under visible-light illumination. The reaction proceeds smoothly, tolerates various functionalities, and was applied for the synthesis of pharmaceutically relevant compounds. Mechanistic investigations, including EPR, NMR, and DFT calculations, support the postulated reaction mechanism.
- Lecroq, William,Bazille, Pierre,Morlet-Savary, Fabrice,Breugst, Martin,Lalevée, Jacques,Gaumont, Annie-Claude,Lakhdar, Sami
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supporting information
p. 4164 - 4167
(2018/07/29)
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- P-arylation of aryl halides by an environmentally compatible method
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In this paper, palladium-DABCO complex supported on magnetic nanoparticles was successfully used as a new magnetically recoverable heterogeneous catalyst for the synthesis of arylphosphonates via P-arylation of different types of aryl halides (aryl iodides/bromides/chlorides and benzene boronic acid/sulfonate), with phosphite esters (triethyl/triphenyl/tri-iso-propyl/diethyl/diphenyl/di-iso-propyl phosphite) in neat water without using any additive. The heterogeneous catalyst was easily isolated from the reaction mixture by an external magnet and reused five times without significant degradation in its activity.
- Sobhani, Sara,Vahidi, Zahra
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p. 1280 - 1284
(2017/11/27)
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- Carbazole compound as Autotaxin inhibitor, preparation method therefor and application of carbazole compound
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The invention belongs to the technical field of biological pharmaceuticals and aims at providing a carbazole compound as an Autotaxin inhibitor, use of the compound in preparation of drugs for targeted inhibition of activity of the Autotaxin, use of the compound in preparation of drugs for treating and preventing diseases or symptoms caused by rising of lysophosphatidic acid and the Autotaxin, and use of the compound in preparation of antitumor drugs. The compound is a 2,7-substituted carbazole derivative, particularly 5-[7-(4-R2-benzyloxy)-9H-carbazol-2-methylene]-2-R1 phenol, R1-SWS-R2 for short, wherein R1 is methyl or ethyl, and R2 is any one of halogen, boric acid, sulfonyl, phospho, carboxyl and amino acid. The compound has very good anti-tumor activity to autocrine high-expression cell lines and has un-obvious influence on low-expression cell lines. The compound can be used for preparing corresponding antitumor drugs and provides possibility for designing novel Autotaxin inhibitors.
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Paragraph 0022; 0027
(2018/01/04)
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- A palladium-catalyzed oxidative cross-coupling reaction between aryl pinacol boronates and H-phosphonates in ethanol
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The first successful oxidative coupling reaction of aryl pinacol boronic esters with H-phosphonates to deliver aryl phosphorous compounds is reported herein. These reactions between aryl boronic reagents and H-phosphonates were carried out synergistically using a Pd catalyst, additive and oxidant. Without using bases and ligands, phosphorylation was accomplished in an environmentally-friendly manner under mild conditions in ethanol.
- Chen, Te-Hsuan,Reddy, Daggula Mallikarjuna,Lee, Chin-Fa
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p. 30214 - 30220
(2017/07/07)
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- Decarbonylative Phosphorylation of Amides by Palladium and Nickel Catalysis: The Hirao Cross-Coupling of Amide Derivatives
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Considering the ubiquity of organophosphorus compounds in organic synthesis, pharmaceutical discovery agrochemical crop protection and materials chemistry, new methods for their construction hold particular significance. A conventional method for the synthesis of C?P bonds involves cross-coupling of aryl halides and dialkyl phosphites (the Hirao reaction). We report a catalytic deamidative phosphorylation of a wide range of amides using a palladium or nickel catalyst giving aryl phosphonates in good to excellent yields. The present method tolerates a wide range of functional groups. The reaction constitutes the first example of a transition-metal-catalyzed generation of C?P bonds from amides. This redox-neutral protocol can be combined with site-selective conventional cross-coupling for the regioselective synthesis of potential pharmacophores. Mechanistic studies suggest an oxidative addition/transmetallation pathway. In light of the importance of amides and phosphonates as synthetic intermediates, we envision that this Pd and Ni-catalyzed C?P bond forming method will find broad application.
- Liu, Chengwei,Szostak, Michal
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p. 12718 - 12722
(2017/10/06)
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- Ar-P bond construction by the Pd-catalyzed oxidative cross-coupling of arylsilanes with H-phosphonates via C-Si bond cleavage
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A novel and efficient methodology that allows for the construction of Ar-P bonds via the Pd-catalyzed oxidative cross-coupling reaction of various arylsilanes with H-phosphonates leading to valuable arylphosphonates has been developed.
- Luo, Haiqing,Liu, Haidong,Chen, Xingwei,Wang, Keke,Luo, Xuzhong,Wang, Kejun
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supporting information
p. 956 - 958
(2017/01/17)
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- A new magnetically recoverable heterogeneous palladium catalyst for phosphonation reactions in aqueous micellar solution
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A new heterogeneous palladium complex of 2-aminothiophenol supported on nanomagnetic γ-Fe2O3 was synthesized and characterized using various methods. The catalyst was used as a magnetically recoverable heterogeneous palladium catalyst for phosphonation reactions via C-P bond formation. Using this method, a wide range of electrophilic benzenes was coupled successfully with phosphite esters (triethyl/tri-isopropyl/triphenylphosphite and diethyl/di-isopropyl/diphenylphosphite) in aqueous micellar solution to generate the corresponding arylphosphonates in good to high yields. The catalyst was separated using an external magnet and reused for six consecutive cycles without any significant loss of its reactivity.
- Sobhani, Sara,Zeraatkar, Zohre
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- Synthesis of arylphosphonates catalyzed by Pd-imino-Py-γ-Fe2O3 as a new magnetically recyclable heterogeneous catalyst in pure water without requiring any additive
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A palladium-Schiff base complex immobilized covalently on γ-Fe2O3 (Pd-imino-Py-γ-Fe2O3) was synthesized and characterized by different methods such as XRD (X-ray diffraction), SEM (scanning electron microscopy), TEM (transmission electron microscopy), FT-IR (Fourier transform infrared spectroscopy), TGA (thermogravimetric analysis), ICP (inductively coupled plasma), XPS (X-ray photoelectron spectroscopy), VSM (vibrating sample magnetometer) and elemental analysis. It was used as a new magnetically recyclable heterogeneous Pd catalyst for the synthesis of arylphosphinates via Csp2-P coupling reactions. A wide range of electrophilic benzenes were coupled successfully with triethylphosphite to generate the corresponding products in good to high yields in pure water without using any additive. The true heterogeneous Pd-imino-Py-γ-Fe2O3 could be reused simply with the aid of a magnetic bar for eight consecutive cycles without any drastic loss of its reactivity.
- Sobhani, Sara,Ramezani, Zohreh
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p. 29237 - 29244
(2018/06/06)
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- Nucleophile promoted gold redox catalysis with diazonium salts: C-Br, C-S and C-P bond formation through catalytic Sandmeyer coupling
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Gold-catalyzed C-heteroatom (C-X) coupling reactions are evaluated without using sacrificial oxidants. Vital to the success of this methodology is the nucleophile-assisted activation of aryldiazonium salts, which could be an effective oxidant for converting Au(i) to Au(iii) even without the addition of an assisting ligand or photocatalyst. By accelerating the reaction kinetics to outcompete C-C homo-coupling or diazonium dediazoniation, gold-catalyzed Sandmeyer reactions were achieved with different nucleophiles, forming C-Br, C-S and C-P bonds in high yields and selectivities.
- Peng, Haihui,Cai, Rong,Xu, Chang,Chen, Hao,Shi, Xiaodong
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p. 6190 - 6196
(2016/09/03)
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- The Cu-catalyzed C-P coupling of phosphonate esters with arylboronic acids
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Copper-catalyzed C-P cross coupling of phosphonate esters with arylboronic acids has been developed. The reaction provided an efficient method for aryl phosphonates under mild conditions.
- Wan,Zhao,Wang,Zhang,Li
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p. 150 - 153
(2016/03/12)
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- MW-Assisted P-C Coupling Reaction Using P-Ligand-Free Pd(OAc) 2 Catalyst
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P-C coupling reactions of a variety of >P(O)H species with aryl bromides were found to take place under P-ligand-free microwave conditions.
- Jablonkai, Erzsébet,Balázs, László B.,Keglevich, Gy?rgy
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p. 660 - 663
(2015/07/20)
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- A dual catalytic strategy for carbon-phosphorus cross-coupling via gold and photoredox catalysis
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A new method for the P-arylation of aryldiazonium salts with H-phosphonates via dual gold and photoredox catalysis is described. The reaction proceeds smoothly at room temperature in the absence of base and/or additives, and offers an efficient approach t
- He, Ying,Wu, Hongmiao,Toste, F. Dean
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p. 1194 - 1198
(2015/01/30)
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- Pd-catalyzed P-arylation of triarylantimony dicarboxylates with dialkyl H-phosphites without a base: Synthesis of arylphosphonates
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The reaction of triarylantimony diacetates [Ar3Sb(OAc)2] with dialkyl H-phosphites [H-PO(OR)2] in the presence of a Pd(PPh3)4 (5 mol%) catalyst led to the formation of arylphosphonates in moderate to excellent yield under base-free conditions. This reaction is the first example of carbon-phosphorus bond formation by using an organoantimony compound as a pseudo-halide.
- Matsumura, Mio,Dong, Yuqiang,Kakusawa, Naoki,Yasuike, Shuji
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p. 130 - 133
(2015/02/19)
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- First reusable ligand-free palladium catalyzed C-P bond formation of aryl halides with trialkylphosphites in neat water
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A reusable ligand-free palladium catalyzed phosphonation of aryl iodides, bromides and chlorides with trialkylphosphites is described for the first time in neat water. The aryl phosphonates are obtained in good to excellent yields. The reaction can be also performed with Ni(II) with longer reaction time. The role of tetrabutylammonium bromide in this reaction as reducing agent for generation of Pd(0) at room temperature is also demonstrated. Pd(0)/TBAB was easily reused for three runs without decreasing the efficiency.
- Iranpoor, Nasser,Firouzabadi, Habib,Rajabi Moghadam, Khashayar,Motavalli, Somayeh
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p. 55732 - 55737
(2015/02/05)
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- A "green" variation of the Hirao reaction: The P-C coupling of diethyl phosphite, alkyl phenyl-H-phosphinates and secondary phosphine oxides with bromoarenes using a P-ligand-free Pd(OAc)2 catalyst under microwave and solvent-free conditions
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The P-C coupling of diethyl phosphite, alkyl phenyl-H-phosphinates, diphenylphosphine oxide and dialkylphosphine oxides with bromoarenes may be performed in the presence of a P-ligand-free Pd(OAc)2 catalyst and triethylamine under microwave-assisted (MW) and, in almost all cases, solvent-free conditions to afford diethyl arylphosphonates, alkyl diphenylphosphinates, aryldiphenylphosphine oxides and dialkylphenylphosphine oxides, respectively. This is the "greenest" accomplishment of the well-known Hirao reaction that has now been found to have general application for a broad spectrum of >P(O)H species with different reactivity and a great variety of substituted bromobenzenes. The alkyl phenyl-H-phosphinates were prepared by the MW-promoted alkylation of phenyl-H-phosphinic acid in the absence of any solvent. This journal is the Partner Organisations 2014.
- Keglevich, Gyoergy,Jablonkai, Erzsebet,Balazs, Laszlo B.
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p. 22808 - 22816
(2014/06/23)
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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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- Palladium-catalyzed desulfitative C-P coupling of arylsulfinate metal salts and H-phosphonates
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Catalyzed by palladium(ii) chloride, a diverse range of arylsulfinate sodium, potassium, lithium, silver, zinc, and copper salts undergo desulfination/C-P coupling with H-phosphonates, in the presence of silver(i) carbonate as oxidant, to produce useful arylphosphonates under microwave irradiation. the Partner Organisations 2014.
- Li, Junchen,Bi, Xiaojing,Wang, Hongmei,Xiao, Junhua
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p. 19214 - 19217
(2014/05/20)
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- Palladium-catalyzed desulfitative cross-coupling reaction of sodium arylsulfinates with H-phosphonate diesters
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A novel and convenient palladium-catalyzed cross-coupling reaction of H-phosphonate diesters with sodium arylsulfinates was developed via desulfitation in the presence of silver carbonate and tetra-butylammonium chloride. This method is highly efficient and provides a rapid access to a broad spectrum of arylphosphonate diesters in good to excellent yields.
- Miao, Tao,Wang, Lei
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supporting information
p. 967 - 971
(2014/04/03)
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- An improved procedure for the synthesis of aryl phosphonates by palladium-catalysed cross-coupling of aryl halides and diethyl phosphite in polyethylene glycol
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A general and greener protocol for the synthesis of aryl phosphonates by the cross-coupling of aryl halides and diethyl phosphite using tetrakis(triphenylphosphine)palladiume/triethylamine/polyethylene glycol 600 [Pd(PPh3)4/ Et3N/PEG 600] as an efficient catalytic system has been developed. This procedure also avoids hazardous solvents and is therefore an eco-friendly alternative to the existing methods.
- Wang, Ping,Lu, Jie,Zhang, Zhan-Hui
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p. 359 - 361
(2013/07/26)
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- P-ligand-free, microwave-assisted variation of the Hirao reaction under solvent-free conditions; The P-C coupling reaction of >p(O)H species and bromoarenes
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Under microwave conditions, the P-C coupling of aryl bromides and >P(O)H species, such as dialkyl phosphites, alkyl aryl-H-phosphinates, or diphenylphosphine oxide takes place in the presence of Pd(OAc)2 as the catalyst and triethylamine as the base without using any P-ligand or solvent. The method described is green and is of more general value.
- Jablonkai, Erzsébet,Keglevich, Gy?rgy
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p. 4185 - 4188
(2013/07/26)
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- Synthesis and proton dissociation properties of arylphosphonates: A microwave-assisted catalytic arbuzov reaction with aryl bromides
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A series of substituted diethyl arylphosphonates was synthesized by the microwave-assisted Arbuzov reaction of triethyl phosphite and aryl bromides in the presence of NiCl2 as the catalyst under solvent-free conditions in good yields. The resulting phosphonates were hydrolyzed to the corresponding arylphosphonic acids whose acidity was evaluated by physicochemical methods.
- Keglevich, Gyoergy,Gruen, Alajos,Boelcskei, Adrienn,Drahos, Laszlo,Kraszni, Marta,Balogh, Gyoergy T.
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p. 574 - 582
(2013/01/15)
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- Nickel-catalyzed C-P coupling of aryl mesylates and tosylates with H(O)PR1R2
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A method was developed for the nickel-catalyzed phosphonylation of aryl mesylates and tosylates with H(O)PR1R2. To the best of our knowledge, this is the first example of nickel-catalyzed C-P coupling of aryl mesylates and tosylates. Most of the substrates gave moderate to good yields under our catalytic system.
- Shen, Chaoren,Yang, Guoqiang,Zhang, Wanbin
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supporting information; experimental part
p. 3500 - 3505
(2012/05/20)
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- Nickel-catalyzed Arbuzov reactions of aryl triflates with triethyl phosphite
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An efficient method was developed for the nickel-catalyzed phosphonylation of aryl triflates with triethyl phosphite, in which KBr as an additive promoted the SN2 catalytic step. To the best of our knowledge, this is the first example of nickel
- Yang, Guoqiang,Shen, Chaoren,Zhang, Liang,Zhang, Wanbin
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supporting information; experimental part
p. 5032 - 5035
(2011/10/09)
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- Solution-deposited organic - Inorganic hybrid multilayer gate dielectrics. Design, synthesis, microstructures, and electrical properties with thin-film transistors
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We report here on the rational synthesis, processing, and dielectric properties of novel layer-by-layer organic/inorganic hybrid multilayer dielectric films enabled by polarizable π-electron phosphonic acid building blocks and ultrathin ZrO2 layers. These new zirconia-based self-assembled nanodielectric (Zr-SAND) films (5 - 12 nm thick) are readily fabricated via solution processes under ambient atmosphere. Attractive Zr-SAND properties include amenability to accurate control of film thickness, large-area uniformity, well-defined nanostructure, exceptionally large electrical capacitance (up to 750 nF/cm2), excellent in ulating properties (leakage current densities as low as 10- 7 A/cm2), and excellent thermal stability. Thin-film transistors (TFTs) fabricated with pentacene and PDIF-CN2 as representative organic semiconductors and zinc - tin - oxide (Zn - Sn - O) as a representative inorganic semiconductor function well at low voltages (±4.0 V). Furthermore, the TFT performance parameters of representative organic semiconductors deposited on Zr-SAND films, functionalized on the surface with various alkylphosphonic acid self-assembled monolayers, are investigated and shown to correlate closely with the alkylphosphonic acid chain dimensions.
- Ha, Young-Geun,Emery, Jonathan D.,Bedzyk, Michael J.,Usta, Hakan,Facchetti, Antonio,Marks, Tobin J.
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experimental part
p. 10239 - 10250
(2011/09/12)
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- Copper-catalyzed C-P bond construction via direct coupling of phenylboronic acids with H-phosphonate diesters
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A mild and efficient method was developed for the copper-catalyzed additions of H-phosphonate diesters to boronic acids under the copper catalyst system Cu2O/1,10-phenanthroline. To the best of our knowledge this finding is the first example of a copper-catalyzed synthesis of aryl phosphonates from arylboronic acids and H-phosphonate dialkyl esters.
- Zhuang, Rongqiang,Xu, Jian,Cai, Zhenshi,Tang, Guo,Fang, Meijuan,Zhao, Yufen
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supporting information; experimental part
p. 2110 - 2113
(2011/06/20)
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- Manganese(III)-mediated direct phosphonylation of arenes
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Manganese (III)-promoted direct phosphonylation of mono- and disubstituted arenes with dialkylphosphite afforded regioselective dialkylphosphonates in good yields. The reactions can apply to arenes bearing electron-donating groups and electron-withdrawing
- Xu, Wei,Zou, Jian-Ping,Zhang, Wei
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experimental part
p. 2639 - 2643
(2010/06/16)
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- Arenediazonium tetrafluoroborates in palladium-catalyzed C-P bond-forming reactions. Synthesis of arylphosphonates, -phosphine oxides, and -phosphines
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A novel palladium-catalyzed synthesis of arylphosphonates from arenediazonium tetrafluoroborates and triethylphosphite or diethylphosphite is presented. The reaction tolerates useful substituents including bromo, chloro, nitro, ether, cyano, keto, and ester groups, can be performed as a one-pot process from anilines omitting the isolation of arenediazonium salts, and can be extended to the preparation of arylphosphine oxides and arylphosphines.
- Berrino, Roberta,Cacchi, Sandro,Fabrizi, Giancarlo,Goggiamani, Antonella,Stabile, Paolo
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supporting information; experimental part
p. 4518 - 4520
(2010/11/17)
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- Microwave-promoted palladium(II)-catalyzed C-P bond formation by using arylboronic acids or aryltrifluoroborates
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The first PdII-catalyzed P arylation has been performed by using palladium acetate, the rigid bidentate ligand dmphen (dmphen=2,9-dimethyl-1,10- phenanthroline), and without the addition of base or acid. Couplings of arylboronic acids or aryl t
- Andaloussi, Mounir,Lindh, Jonas,Saevmarker, Jonas,Sjoeberg, Per J. R.,Larhed, Mats
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supporting information; experimental part
p. 13069 - 13074
(2010/05/19)
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- Development of a room temperature Hirao reaction
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Arylphosphonates were prepared at 25 °C through the palladium-catalyzed coupling of aryl iodides with a silver phosphonate. A wide range of aryl iodides were successfully employed including phenolic substrates as well as those containing an ortho substitu
- Kohler, Mark C.,Sokol, Joseph G.,Stockland Jr., Robert A.
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supporting information; body text
p. 457 - 459
(2009/05/27)
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- Phosphonation of arenes with dialkyl phosphites catalyzed by Mn(II)/Co(II)/O2 redox couple
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Arylphosphonates were first synthesized through a catalytic phosphonation of various arenes with dialkyl phosphites under the influence of an Mn(OAc) 2/Co(OAc)2/O2 redox couple. For instance, the reaction of benzene with d
- Kagayama, Takashi,Nakano, Atsushi,Sakaguchi, Satoshi,Ishii, Yasutaka
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p. 407 - 409
(2007/10/03)
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- A versatile and efficient ligand for copper-catalyzed formation of C-N, C-O, and P-C bonds: Pyrrolidine-2-phosphonic acid phenyl monoester
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A new and readily available bidentate ligand, namely, pyrrolidine-2- phosphonic acid phenyl monoester (PPAPM), has been developed for the copper-catalyzed formation of C-N, C-O, and P-C bonds, and various N-, O-, and P-arylation products were synthesized in good to excellent yields by using the CuI/PPAPM catalyst system. Addition of the PPAPM ligand greatly increases the reactivity of the copper catalyst, and the resulting versatile and efficient catalyst system is of widespread and practical application in cross-coupling reactions.
- Rao, Honghua,Jin, Ying,Fu, Hua,Jiang, Yuyang,Zhao, Yufen
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p. 3636 - 3646
(2008/02/03)
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- Proline/pipecolinic acid-promoted copper-catalyzed P-arylation
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We have developed a convenient and efficient approach for P-arylation of organophosphorus compounds containing P-H. Using commercially available and inexpensive proline and pipecolinic acid as the ligands greatly improved the efficiency of the coupling reactions, so the method can provide an entry to arylphosphonates, arylphosphinates and arylphosphine oxides.
- Huang, Cheng,Tang, Xu,Fu, Hua,Jiang, Yuyang,Zhao, Yufen
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p. 5020 - 5022
(2007/10/03)
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- Practical protocol for the palladium-catalyzed synthesis of arylphosphonates from bromoarenes and diethyl phosphite
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A greatly improved, reliable protocol for the palladium-catalyzed cross-coupling of dialkyl phosphites with aryl bromides has been developed. The use of an alcoholic solvent was the key to high yields in the synthesis of a broad variety of arylphosphonate
- Goo?en, Lukas J.,Dezfuli, Mohammad K.
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p. 445 - 448
(2007/10/03)
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- Structure-Activity Relationships of Small Phosphopeptides, Inhibitors of Grb2 SH2 Domain, and Their Prodrugs
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To develop potential antitumor agents directed toward HER2/ErbB2 overexpression in cancer, we have designed inhibitors of the recognition between the phosphotyrosine of the receptor and the SH2 domain of the adaptor protein Grb2. In the first part of the paper, we report the synthesis of mimetics of the constrained (α-Me)phosphotyrosine residue such as (α-Me)-4-phosphonomethylphenylalanine (-CH2PO3H 2), (α-Me) 4-phosphonodifluoromethylphenylalanine (-CF 2PO3H2), and (α -Me)-4-phosphonophenylalanine (-PO3H2). The incorporation of these residues in the mAZ-pTyr-Xaa-Asn-NH2 series provided compounds with very high affinity for the Grb2 SH2 domain, in the 10 -8-10-9 range of Kd values. These compounds behave as potent antagonists of the Grb2-Shc interaction. Our results highlight the importance of the doubly negative charge borne by the pY + 1 amino acid in accordance with the interactions observed in the complex crystallized between mAZ-pTyr-(αMe)pTyr-Asn-NH2 and the Grb2 SH2 domain. mAZ-pTyr-(αMe)pTyr-Asn-NH2 was derivatized as the S-acetyl thioester (SATE) of the phosphotyrosine residues, and its surrogates provided prodrugs with very potent antiproliferative activity on cells overexpressing HER2/ErbB2, with ED50 values amounting to 0.1 μM. Finally a new prodrug is put forth under the form of a monobenzyl ester of phosphate group that is as active as and much easier to synthesize than SATE prodrugs. These compounds show promising activity for further testing on in vivo models.
- Liu, Wang-Qing,Vidal, Michel,Olszowy, Catherine,Million, Emmanuelle,Lenoir, Christine,Dh?tel, Hélène,Garbay, Christiane
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p. 1223 - 1233
(2007/10/03)
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- NOVEL BENSOPHENONE DERIVATIVES OR SALTS THEREOF
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A benzophenone derivative represented by the following formula: whereinR1 represents, for example, an optionally substituted heterocyclic group, or a substituted phenyl group; Z represents, for example, an alkylene group; R2 represents, for example, a carboxyl group optionally protected with alkyl;R3 represents, for example, an optionally protected hydroxyl group; R4 represents, for example, an optionally substituted cycloalkyloxy group; and R5 represents, for example, a hydrogen atom, ???or a salt thereof has anti-arthritic activity, inhibits bone destruction caused by arthritis, and provides high safety and excellent pharmacokinetics and thus is useful as therapeutic agent for arthritis. These compounds have inhibitory effect on AP-1 activity and are useful as preventive or therapeutic agent for diseases in which excessive expression of AP-1 is involved.
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- Nickel and palladium catalysed reaction of triethyl phosphite with aryl halides under microwave irradiation
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Diethyl aryl phosphonates are efficiently and rapidly obtained from halides and triethyl phosphite without solvent. The reaction was catalysed by NiCl2 or PdCl2 (10%) under focussed microwave radiation.
- Villemin, Didier,Elbilali, Abdelghani,Simeon, Fabrice,Jaffres, Paul-Alain,Maheut, Geraldine,Mosaddak, Mahjouba,Hakiki, Abdelhack
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p. 436 - 437
(2007/10/03)
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- New type of metalloproteinase inhibitor: Design and synthesis of new phosphonamide-based hydroxamic acids
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A series of phosphonamide-based hydroxamate derivatives were synthesized, and the inhibitory activities were evaluated against various metalloproteinases in order to clarify its selectivity profile. Among the four diastereomeric isomers resulting from the
- Sawa, Masaaki,Kiyoi, Takao,Kurokawa, Kiriko,Kumihara, Hiroshi,Yamamoto, Minoru,Miyasaka, Tomohiro,Ito, Yasuko,Hirayama, Ryoichi,Inoue, Tomomi,Kirii, Yasuyuki,Nishiwaki, Eiji,Ohmoto, Hiroshi,Maeda, Yu,Ishibushi, Etsuko,Inoue, Yoshimasa,Yoshino, Kohichiro,Kondo, Hirosato
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p. 919 - 929
(2007/10/03)
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- Pseudopeptide compounds having an inhibiting activity with respect to paths activated by proteins with active tyrosine kinase activity and pharmaceutical compositions containing same
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The invention concerns a compound corresponding to general formula (1) wherein, in particular, R2 represents a phenylmethyl or naphthylmethyl or cyclohexylmethyl radical, 2- and 3-pryidinylmethyl, substituted on the cycle in meta or para positi
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