- 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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- 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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- Nickel-Catalyzed Phosphorylation of Tosylates
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Abstract: Four new bidentate phosphine ligands have been synthesized, characterized and evaluated in Ni-catalyzed C–P coupling reaction. The readily available and inexpensive highly active sulfonate Ni(cod)2-L8 catalyzes the reaction leading to
- Li, Chun-jing
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p. 725 - 730
(2020/06/30)
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- Cobalt catalyzed C-P bond formation by cross-coupling of boronic acids with P(O)H compounds in presence of zinc
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In our current work, we have reported the first cobalt-catalyzed cross-coupling of arylboronic acid with alkyl/aryl phosphites under mild conditions. The reaction was carried out in the presence of zinc powder as an additive and ter-pyridine as a ligand. The use of non-precious cobalt salt makes the protocol advantageous, as it is inexpensive and more abundant than the previously used methods where precious metal salts (Pd and Pt) were used. The reaction has a wide substrate scope and the products were obtained in good yields.
- Hicks, Ian,McTague, Jonathan,Hapatsha, Tatiana,Teriak, Rania,Kaur, Parminder
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- Synthesis, characterization and properties of titanium phosphonate clusters
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Titanium phosphonate clusters were synthesized by the reactions of titanium tetraisopropoxide (Ti(OiPr)4) with arylphosphonic acids (ArPO3H2, Ar = Ph, 1-Nap, 4-MeOPh, 4-FPh, 4-ClPh, 4-BrPh, and 4-BrBn) and H2O in tetrahydrofuran (THF) at room temperature. [Ti4(μ3-O)(OiPr)5(μ-OiPr)3(O3PAr)3]·solv (Ar = Ph (1), 1-Nap (2), 4-MeOPh (3), 4-FPh (4), 4-ClPh (5); solv = thf for 1 and 2 or 2-propanol for 3–5) were isolated as new Ti4P3-type clusters, while Ti7(μ3-O)2(OiPr)6(μ-OiPr)6(O3PBnBr)6 (6) was isolated as a Ti7P6-type cluster. A co-crystal of Ti4P3- (7a) and Ti7P6-type (7b) clusters were obtained when 4-BrPhPO3H2 was used, and [Ti(OiPr)(acac)(O3PPh)]4 (8), a new cage cluster, was obtained when Ti(acac)2(OiPr)2 (Hacac = acetylacetone) was reacted with PhPO3H2.
- Hayami, Ryohei,Sagawa, Takuya,Tsukada, Satoru,Yamamoto, Kazuki,Gunji, Takahiro
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supporting information
p. 1 - 8
(2018/04/02)
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- Avisible-light-promoted metal-free strategy towards arylphosphonates: Organic-dye-catalyzed phosphorylation of arylhydrazines with trialkylphosphites
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A visible-light-induced metal-free catalytic system was developed for the synthesis of arylphosphonates starting from arylhydrazines and trialkylphosphites. By using the inexpensive eosin B as catalyst, sub-stoichiometric amounts of DABCO, and ambient air as oxidant, diverse arylphosphonates were obtained under visible-light irradiation. Notably, this catalytic system is suitable for gram-scale reaction by utilizing sunlight as an illumination source.
- Li, Rui,Chen, Xiaolan,Wei, Shengkai,Sun, Kai,Fan, Lulu,Liu, Yan,Qu, Lingbo,Zhao, Yufen,Yu, Bing
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supporting information
p. 4807 - 4813
(2018/12/11)
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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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- 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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- 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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- 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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- 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 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 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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- 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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- 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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- Phosphoryl-related directing groups in rhodium(III) catalysis: A general strategy to diverse P-containing frameworks
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Herein, a rhodium(III)-catalyzed oxidative C-H activation of simple arylphosphonates and phosphonamides with subsequent coupling with alkenes (olefination), internal alkynes (hydroarylation and oxidative cyclization), or simple arenes to give access to diverse P-containing functional frameworks is reported.
- Zhao, Dongbing,Nimphius, Corinna,Lindale, Matthew,Glorius, Frank
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supporting information
p. 4504 - 4507
(2013/09/24)
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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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- 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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- 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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- Preparation of arylphosphonates by palladium(O)-catalyzed cross-coupling in the presence of acetate additives: Synthetic and mechanistic studies
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An efficient protocol for the synthesis of arylphosphonate diesters via a palladium-catalyzed cross-coupling of H-phosphonate diesters with aryl electrophiles, promoted by acetate ions, was developed. A significant shortening of the cross-coupling time in the presence of the added acetate ions was achieved for bidentate and monodentate supporting ligands, and for different aryl electrophiles (iodo, bromo and triflate derivatives). The reaction conditions were optimized in terms of amount of the catalyst, supporting ligands, and source of the acetate ion used. Various arylphosphonates, including those of potential biological significance, were synthesized using this newly developed protocol. Some mechanistic aspects of the investigated reactions are also discussed.
- Kalek, Marcin,Jezowska, Martina,Stawinski, Jacek
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experimental part
p. 3207 - 3216
(2010/04/26)
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- Synthesis and coordination chemistry of fluorinated phosphonic acids
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Phosphonic acids [(HO)2P(O)C2H4CnF2n+1] (n = 4, 6) and [(HO)2P(O)C6H4-4-CnF2n+1] (n = 0, 1, 6) have been prepared in good yields. Deprotonation a
- Bennett, James A.,Hope, Eric G.,Singh, Kuldip,Stuart, Alison M.
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experimental part
p. 615 - 620
(2009/12/07)
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- INHIBITORS OF TYROSINE KINASES AND USES THEREOF
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Disclosed herein are compounds that inhibit the activity of particular tyrosine kinases. Methods for the preparation of such compounds are disclosed. Also disclosed are pharmaceutical compositions that include the compounds. Methods of using the compounds disclosed, alone or in combination with other therapeutic agents, for the treatment of tyrosine kinase-rnediated diseases or conditions or tyrosine, kinase-dependent diseases or conditions are provided.
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Page/Page column 103
(2008/06/13)
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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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- 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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- Water soluble phosphines
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This invention relates to water soluble phosphines of the following structural formula and method of preparing these phosphines: Wherein A is a moiety which is stable to the reaction conditions and does not interfere with solubility of the compound in the
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- Novel Syntheses of Mono- and Bisphosphonated Aromatic Phosphanes by Consecutive Pd-Catalyzed P-C Coupling Reactions and Nucleophilic Phosphanylation - X-ray Structure of Ph2P-C6H4-m-PO3Na2 · 5.5 H2O · iPrOH
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The triphenylphosphane derivatives 2a and 5, bearing one and two phosphonic ester groups, are accessible in high yields by consecutive Pd-catalyzed P-C coupling reactions of p-bromoiodobenzene with Ph2PH and PhPH2, respectively, and then with diethyl phosphite. Ester hydrolysis yields the highly water-soluble sodium salts of mono- and bisphosphonated triphenylphosphane, 3a and 6, respectively. On reaction of the p- and m-fluorophenylphosphonic diethyl esters 7a, 7b with Ph2PK and subsequent ester hydrolysis the isomeric disodium (diphenylphosphano)phenylphosphonates 3a, 3b were obtained. The X-ray structure of Ph2P(C6H4-m-PO3Na2) · 5.5 H2O · iPrOH (space group Cmc21) has been determined. In the solid state, it forms a layer structure with hydrophilic (PO32-, H2O, iPrOH) and hydrophobic (Ph2P) compartments, in which the PO32- anionic groups are not engaged in coordination of the sodium cations.
- Machnitzki, Peter,Nickel, Thomas,Stelzer, Othmar,Landgrafe, Claudia
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p. 1029 - 1034
(2007/10/03)
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- Oxidative Phoshonylation of Aromatics with Ammonium Cerium(IV) Nitrate
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Arylphosphonates 5 and 6 can be prepared in good yields in a one-step synthesis starting from arenes with tri- or diethylphosphites and cerium ammonium nitrate (CAN) as oxidant.The seletivity of the oxidative phosphonylation is relatively low; the reactive species is a phosphite radical cation.
- Kottmann, Hariolf,Skarzewski, Jacek,Effenberger, Franz
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p. 797 - 801
(2007/10/02)
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- OXIDATIVE PHOSPHONYLATION OF AROMATIC COMPOUNDS
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Aryl phosphonates can be prepared in good yield from the respective arenes and tri- or dialkylphosphites by either chemical or anodic oxidation.The anodic oxidation proceeds either via phosphinium radical cations, which then attack the arenes electrophilically, or via arene radical cations, which add the trialkylphosphite as nucleophile.Aryl phosphonates are also obtained in good yield by chemical oxidation with peroxodisulfate/AgNO3 in acetonitrile/water or glacial acetic acid.The diethylphosphinium radical cation, formed from diethylphosphite by oxidation with Ag(II), is supposed to be the reactive species in this process.Raising the silver salt concentration leads to an increase in polyphosphonylation.Selectivity ratios were determined for the oxidative phosphonylation process.
- Effenberger, Franz,Kottmann, Hariolf
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p. 4171 - 4182
(2007/10/02)
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- THE EFFECT OF ORTHO SUBSTITUENTS IN SRN1 REACTIONS. SOME SYNTHETIC APPLICATIONS.
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Several ortho-substituted iodobenzenes were allowed to react, via the SRNl mechanism, with mixtures of diethyl phosphite ion and pinacolone enolate ion.From product composition data, the relative reactivities of the two nucleophiles were reckoned.They represent relative reactivities in attachment to aryl radical intermediates.Most of the ortho effects are slight, but there is evidence that large ortho substituents hinder attachment of the phosphite more than the enolate nucleophile.The methoxy and diethoxyphosphoryl substituents, when para to the site of substitution, respectively favour and disfavour the phosphite with respect to the enolate ion.SRNl reactions of ortho-substituted halobenzenes are, for some substituents, followed by other reactions which afford products of synthetic interest.
- Bunnett, Joseph F.,Mitchel, Eric,Galli, Carlo
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p. 4119 - 4132
(2007/10/02)
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- Effect of para Substituents on Decomposition Rates of 2-(N,N'-Dimethylamino)ethyl Phenyl Phenylphosphonates
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Spontaneous decomposition of nineteen of the title phosphonates to their 1,1,4,4-tetramethylpiperazinium salts was followed in 50 percent aqueous ethanol at different temperatures.The effect of substituents of the phenyl group on reaction rates was about
- Manninen, P. Antti
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p. 635 - 640
(2007/10/02)
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