- Phosphorylation of (1-aryl-1-hydroxymethyl)phosphonates
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The reaction of dimethyl (1-aryl-1-hydroxymethyl)phosphonates with 1-chloro-3-phospholene 1-oxides, diphenylphosphinic chloride or diphenyl chloridophosphonate affords the corresponding (1-phosphoryloxymethyl)phosphonates. The products with two different
- Rádai, Zita,Hodula, Viktória,Kiss, Nóra Zsuzsa,Kóti, János,Keglevich, Gy?rgy
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- Biocatalytic Promiscuity of Lipases in Carbon-Phosphorus Bond Formation
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A promiscuous lipase-catalyzed carbon-phosphorus bond formation is presented. The developed enzymatic Pudovik-Abramov reaction of various aromatic and aliphatic aldehydes with dialkyl phosphonates provides biologically and pharmacologically relevant α-hyd
- Koszelewski, Dominik,Ostaszewski, Ryszard
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- Rational synthesis of α-hydroxyphosphonic derivatives including dronic acids
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New, green methods have been elaborated for the syntheses of α-hydroxyphosphonates and α-hydroxymethylenebisphosphonic derivatives (HMBPs, dronates). α-Hydroxyphosphonates were prepared via the Pudovik reaction, while the synthesis of HMBPs has been performed in the three-component reaction of carboxylic acids, phosphorus trichloride and phosphorus acid.
- Grün, Alajos,Rádai, Zita,S?regi-Nagy, Dávid Illés,Greiner, István,Keglevich, Gy?rgy
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- Superparamagnetic magnesium ferrite nanoparticles: A magnetically reusable and clean heterogeneous catalyst
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A highly efficient magnetically recoverable nano-catalyst was fabricated. The material synthesized has been fully characterized by vibrating sample magnetometry (VSM), X-ray powder diffraction, scanning and transmission electron microscopy, FT-IR, and the
- Sheykhan, Mehdi,Mohammadnejad, Hossein,Akbari, Jafar,Heydari, Akbar
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- Synthesis and anticancer cytotoxicity with structural context of an α-hydroxyphosphonate based compound library derived from substituted benzaldehydes
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We synthesized substituted benzaldehyde derived α-hydroxyphosphonates (αOHP), α-hydroxyphosphonic acids (αOHPA) and α-phosphinoyloxyphosphonates (αOPP) and characterized their cytotoxicity against a panel of cancer cell lines. A library containing 56 analogues was screened against Mes-Sa parental and Mes-Sa/Dx5 multidrug resistant uterine sarcoma cell lines, using a fluorescence-based cytotoxicity assay. The cytotoxicity screening revealed that dibenzyl-αOHPs and dimethyl-α-diphenyl-OPPs were the most active clusters, which encouraged us to synthesize further dibenzyl-α-diphenyl-OPP derivatives that elicited pronounced cell killing. Further structure-activity relationships showed the relevance of hydrophobicity and the position of substituents on the main benzene ring as determinants of toxicity. The most active analogs proved to be equally, or even more toxic to the multidrug resistant (MDR) cell line Mes-Sa/Dx5, suggesting these compounds may overcome P-glycoprotein mediated multidrug resistance by evading the drug transporter.
- Rádai, Zita,Windt, Tímea,Nagy, Veronika,Füredi, András,Kiss, Nóra Zsuzsa,Ranelovi?, Ivan,Tóvári, József,Keglevich, Gy?rgy,Szakács, Gergely,Tóth, Szilárd
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supporting information
p. 14028 - 14035
(2019/09/18)
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- Ultrasound assisted green synthesis of α-hydroxyphosphonates under solvent-free conditions
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Abstract: A simple, efficient and environmentally benign method for the synthesis of α-hydroxyphosphonates by reaction of an aldehyde or a ketone, and trialkylphosphite is effectively accomplished under ultrasound irradiation and solvent-free and catalyst
- Bouzina, Abdeslem,Aouf, Nour-eddine,Berredjem, Malika
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p. 5993 - 6002
(2016/06/01)
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- Synthesis and insecticidal activities of O,O-dialkyl-2-[3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carbonyloxy] (aryl) methylphosphonates
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A series of novel O,O-Dialkyl-2-[3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carbonyloxy](aryl) methy-lphosphonates I-1–14 were designed and synthesized. The structures of all the title compounds were confirmed by 1H-NMR, 13C-NMR, 31P-NMR, IR and elemental analysis. Their insecticidal activities against Mythimna separata and Plutella xylostella were evaluated. The results of bioassays indicated that the title compounds exhibited 20–80% larvicidal activity against Mythimna separata at 1000?mg/L.
- Wang, Wei,Wang, Lie-Ping,Ning, Bin-Ke,Mao, Ming-Zhen,Xue, Chao,Wang, Hai-Yang
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p. 1362 - 1367
(2016/09/28)
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- Phospha-Michael Addition to in Situ Prepared 5-Arylmethylidene Meldrum's Acids
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Knoevenagel condensation reaction of an aldehyde and Meldrum's acid produces a 5-arylmethylidene Meldrum's acid, which undergoes Michael addition of a trialkyl phosphite under solvent-free conditions to afford the title compounds in good yields.
- Adib, Mehdi,Sheikhi, Ehsan,Rezaei, Narjes,Bijanzadeh, Hamid Reza,Mirzaei, Peiman
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p. 1331 - 1334
(2014/06/10)
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- Magnetic Fe3O4 nanoparticle-supported phosphotungstic acid as a recyclable catalyst for the kabachnik-fields reaction of isatins, imines, and aldehydes under solvent-free conditions
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Magnetic-nanoparticle-supported phosphotungstic acid has been used to efficiently catalyze the hydrophosphonylation reaction of isatins, imines, and aldehydes using dimethyl and diethyl phosphite as a nucleophile to give the corresponding α-hydroxy and α-amino phosphonates in excellent yields for a wide range of substrates. The reaction conditions were simple, green, and efficient. The catalyst was recycled up to five times with retention of its activity. Based on the NMR spectroscopy studies, a probable catalytic cycle was proposed.
- Nazish, Mohd,Saravanan,Khan, Noor-Ul H.,Kumari, Prathibha,Kureshy, Rukhsana I.,Abdi, Sayed H. R.,Bajaj, Hari C.
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p. 1753 - 1760
(2015/02/02)
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- Mechanistic approach for expeditious and solvent-free synthesis of α-hydroxy phosphonates using potassium phosphate as catalyst
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An extremely simple, high yielding, highly rapid and solvent-free protocol has been described for hydrophosphylation of aldehydes using potassium phosphate as catalyst. Easy commercial availability of the reusable catalyst, operational simplicity at ambie
- Kulkarni, Makarand A.,Lad, Uday P.,Desai, Uday V.,Mitragotri, Satish D.,Wadgaonkar, Prakash P.
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p. 148 - 152
(2013/04/24)
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- Synthesis, characterization and catalytic properties of magnetic nanoparticle supported guanidine in base catalyzed synthesis of α-hydroxyphosphonates and α-acetoxyphosphonates
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Magnetic nanoparticle Fe3O4-immobilized guanidine (MNPs-Guanidine) as a novel magnetically interphase nanocatalyst was synthesized and characterized. MNPs-Guanidine catalyzed the synthesis of α-hydroxyphosphonates from aldehydes and
- Rostami, Amin,Atashkar, Bahareh,Moradi, Darush
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- MgCl2/Et3N base system as a new catalyst for the synthesis of α-hydroxyphosphonate
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An efficient and simple synthesis of α-hydroxyphosphonates via reaction of aldehydes and ketones with dimethylphosphite in the presence of MgCl2/Et3N base system is reported. The use of readily available and easy to handle reagent MgCl2/Et3N makes this method simple, convenient, and practical. Copyright
- Tajbakhsh, Mahmood,Khaksar, Samad,Tafazoli, Zahra,Bekhradnia, Ahmadreza
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experimental part
p. 827 - 829
(2012/05/21)
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- Synthesis and herbicidal activity of O,O-dimethyl-(3-phenacryloyloxy) alkyl phosphonates
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In an attempt to discover novel compounds with high biological activity and low toxicity, a series of new O,O-dimethyl-(3-phenacryloyloxy) alkyl phosphonates 4a-m have been designed and synthesized by the reaction of 3-phenacryloyl chloride with α-hydroxyalkyl phosphonate. All new compounds were characterized by elemental analysis, IR, and 1H NMR spectroscopy as well as by mass spectrometry. The results of preliminary bioassay indicate that some of the target compounds have excellent inhibitory activities on Triticum aestivum (wheat) and Brassica napus L. (rape). Copyright Taylor and Francis Group, LLC.
- Wang, Tao,Huang, Hai Jin,Luo, Jin,Yu, Dan Hong
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scheme or table
p. 135 - 141
(2012/05/04)
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- N-heterocyclic carbene catalyzed hydrophosphonylation of aldehydes
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N-Heterocyclic carbene catalyzed Pudovik-type reaction of dimethyl trimethylsilyl phosphite and aldehydes for the construction of carbon-phosphorus bonds have been developed, providing -hydroxyphosphonates in moderate to excellent yield. Georg Thieme Verl
- Cai, Zhi-Hua,Du, Guang-Fen,He, Lin,Gu, Cheng-Zhi,Dai, Bin
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experimental part
p. 2073 - 2078
(2011/08/05)
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- Reactions of acyl phosphonates with organoaluminum reagents: A new method for the synthesis of secondary and tertiary α-hydroxy phosphonates
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The reactions of organoaluminum reagents (trimethylaluminum, triethylaluminum, etc.) with aryl and alkyl acyl phosphonates, which lead to the formation of α-hydroxy phosphonates in moderate to good yields, are reported. This method provides easy access to
- Seven, Ozlem,Polat-Cakir, Sidika,Hossain, Md. Shakhawoat,Emrullahoglu, Mustafa,Demir, Ayhan S.
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p. 3464 - 3469
(2011/06/19)
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- Synthesis and herbicidal activity of novel dialkoxyphosphoryl aryl methyl 2-(4,6-dimethoxypyrimidin-2-yloxy) benzoate derivatives
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A series of dialkoxyphosphoryl aryl methyl 2-(4,6-dimethoxy-pyrimidin-2- yloxy) benzoate derivatives was designed and synthesized. All new compounds were identified by elemental analysis, infrared (IR), 1H-NMR, and mass spectrometry (MS). Their herbicidal
- Jin, Chuanfei,He, Hongwu
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experimental part
p. 1397 - 1403
(2011/10/04)
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- Microwave-assisted synthesis of α-hydroxybenzylphosphonates and -benzylphosphine oxides
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A series of α-hydroxy-benzylphosphonates and -benzylphosphine oxides was synthesized by the Na2CO3-catalyzed microwave-assisted addition of dialkyl phosphites and dipenylphosphine oxide to P-substituted benzaldehydes. The solventless reaction provided the products in short reaction times and in 71-88% yield.
- Keglevich, Gyoergy,Toth, Viola Roza,Drahos, Laszo
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experimental part
p. 15 - 17
(2011/10/09)
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- Pyridine 2,6-dicarboxylic acid as a bifunctional organocatalyst for hydrophosphonylation of aldehydes and ketones in water
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A novel organocatalytic, direct synthesis of α-hydroxy phosphonates via reaction of aldehydes and ketones with trimethylphosphite in the presence of catalytic amounts of pyridine 2,6-dicarboxylic acid in water is reported. The method is simple, cost-effec
- Jahani, Fatemeh,Zamenian, Behi,Khaksar, Samad,Tajbakhsh, Mahmood
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experimental part
p. 3315 - 3318
(2010/11/18)
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- Synthesis and biological activity of O,O-Dimethyl-2,6-Pyridinyl diformyloxy alkyl phosphonates
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In an attempt to discover novel compounds with high activity and low toxicity, a series of new O,O-dimethyl-2,6-pyridinyl diformyloxy alkyl phosphonates 4a-4p has been designed and synthesized by the reaction of 2,6-pyridinyl diformyloxy chloride with α-hydroxyalkyl phosphonate. The structures of all new compounds were characterized by elementary analysis, IR, 1H NMR, and MS spectroscopies. The results of a preliminary bioassay indicate that some of the target compounds have obviously promotive action for plant growth against the stalk of barnyard grass.
- Wang, Tao,Lei, Da You,Huang, Ying,Ao, Li Hua
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scheme or table
p. 2777 - 2785
(2010/04/03)
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- The preparation of dimethyl α-hydroxyphosphonates and the chemical shift non-equivalence of their diastereotopic methyl ester groups
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Dimethyl α-hydroxyalkyl-, α-hydroxybenzyl-, α-hydroxyfurfuryl-, and α-hydroxy-α-thienylmethyl-phosphonates have been prepared in good yield by the alumina-catalyzed reaction of dimethyl phosphite with the corresponding alkanals, aryl aldehydes (or aryl methyl ketones), furfuraldehyde, and 2- or 3-thiophenecarboxaldehyde, respectively, thus confirming the general utility of this synthetic procedure. The 1H and 13C nmr spectra of the products exhibit characteristic chemical shift non-equivalence of the diastereotopic methyl ester groups, for which a tentative order of non-equivalence is reported and discussed. Copyright Taylor & Francis Group, LLC.
- Hudson, Harry R.,Yusuf, Ramon O.,Matthews, Ray W.
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experimental part
p. 1527 - 1540
(2009/05/30)
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- Synthesis and herbicidal activity of α-[2-(fluoro-substituted phenoxy)propionyloxy] alkyl phosphonates
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Eight of novel fluoro-substituted phosphonate derivatives were synthesized and the preliminary bioassay indicated that these compounds exhibited herbicidal activities. Copyright Taylor & Francis Group, LLC.
- Li, Yan-Jun,He, Hong-Wu
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body text
p. 712 - 713
(2009/04/05)
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- Phospho-transfer catalysis on the asymmetric hydrophosphonylation of aldehydes
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We report here a precise, in situ 31P{1H}-NMR method of assaying enantiopurity of α-hydroxyphosphonate esters, the products of the carbonyl hydrophosphonylation (Pudovik) reaction. This method is based upon a diazaphospholidine chiral derivatising agent (CDA) which satisfies all of the criteria for a precise assay; (i) derivatisation of α-hydroxyphosphonate esters is both rapid and clean, (ii) kinetic resolution is absent and (iii) 31P{1H} chemical shift dispersions are excellent (> 5ppm). Calibration of this assay has been achieved by cross-referencing the 31P{1H}-NMR signals obtained for the CDA-derivatised ester of (MeO)2PC=O)CHPh(OH) to optical rotation measurements from scalemic material obtained upon lipase catalysed hydrolysis (F-AP 15, Rhizopus oryzae) of (MeO)2P(=O)CHPh(OAc). Analysis of NMR chemical shift and coupling parameters for a closely related series of derivatised α-hydroxyphosphonate esters support further configuration assignments on the basis of inference. We report also on the configurational stability of α-hydroxyphosphonate esters in the presence of acids, organonitrogen bases and metal salts. 2H-labelling and carbonyl crossover experiments reveal that low levels of epimerisation (α) of α-hydroxyphosphonate esters is possible under certain conditions of catalysis and within certain limits. A design strategy for the construction of catalyst systems in the Pudovik reaction is outlined based upon a combination of Lewis acidic (E) and Lewis basic (N) sites. Four types of catalyst are outlined, members of two distinct Classes I and II according to the nature of the acid and base sites, along with our investigations of representative examples of each Class. A variety of Class I.1 systems based on β-amino alcohols (one hydrogen bonding E site and one organonitrogen N site), have been assayed in the model reaction between (MeO)2P(O)H and PhCHO. Results suggest that catalysis of the Pudovik reaction is clean and efficient in certain cases but that catalytic activity is strongly dependent upon the nature of the basic (N) nitrogen centre. Moreover, only low levels ( 50% more strongly (K11 0.53 mol-1 dm3) than dimethyl-H-phosphonate (K11 0.34 mol-1 dm3, 298 K) and to catalyse the hydrophosphonylation reaction between these two substrates with a second order rate constant comparable to that of triethylamine (both k2 5.9 × 10-2 mol-1 dm3 h-1, 293 K). However, one of the major limitations of this model is that competitive product inhibition dominates after some 15 turnovers (75% completion). Model studies reveal that hydrophosphonylation catalysis via a nitrogen Lewis base is accelerated up to 10-fold upon the introduction of [Zn(OSO2CF3)2] as co-catalyst. Consequently, Class II.1 systems employ metal salts [Zn(OSO2CF3)2] as Lewis acidic E sites and chiral co-catalysts capable of binding to the metal and also acting as Lewis basic N sites. Such systems catalyse the addition of (MeO)2P(O)H to PhCHO cleanly with modest turnover numbers (2P(O)H to PhCHO to afford (MeO)2P(O)CHPh(OH) with an average turnover rate (over a 1 h reaction time at 298 K) of 115 h-1 compared to ca. 1 h-1 for NEt3 under analogous conditions. Chiral variants are proposed.
- Davies, Stephen R.,Mitchell, Michael C.,Cain, Christopher P.,Devitt, Paul G.,Taylor, Roger J.,Kee, Terence P.
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- Accurate In Situ 31P Assay of Enantiopurity in α-Hydroxyphosphonate Esters using a Diazaphospholidine Derivatizing Agent
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A rapid, convenient and efficient in situ assay of enantiomeric excess in α-hydroxyphosphonate esters is reported exploiting 31P NMR analysis of the diastereoisomers formed upon condensation with a phosphorochloridite reagent containing a chiral diazaphospholidine ring.Use of this chiral framework affords chemical shift dispersions > 5 ppm between diastereoisomers, Accurate integrations are thus possible once account is taken of differential n.O.e. effects and spin lattice T1 relaxation times of the phosphorus nuclei.
- Devitt, Paul G.,Mitchell, Michael C.,Weetman, John M.,Taylor, Roger J.,Kee, Terence P.
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p. 2039 - 2044
(2007/10/03)
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