- Asymmetric synthesis of stereogenic phosphorus P(V) centers using chiral nucleophilic catalysis
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Organophosphates have been widely used in agrochemistry, as reagents for organic synthesis, and in biochemistry. Phosphate mimics possessing four unique substituents, and thereby a chirality center, are useful in transition metal catalysis and as nucleotide therapeutics. The catalytic, stereocontrolled synthesis of phosphorus‐stereogenic centers is challenging and traditionally depends on a resolution or use of stochiometric auxiliaries. Herein, enantioenriched phosphorus centers have been synthesized using chiral nucleophilic catalysis. Racemic H‐phosphinate species were coupled with nucleophilic alcohols under halogenating conditions. Chiral phosphonate products were synthesized in acceptable yields (33–95%) and modest enantioselectivity (up to 62% ee) was observed after identification of an appropriate chiral catalyst and optimization of the solvent, base, and temperature. Nucleophilic catalysis has a tremendous potential to produce enantioenriched phosphate mimics that could be used as prodrugs or chemical biology probes.
- Brichacek, Matthew,Numan, Ahmed
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- Continuous flow esterification of a H-phosphinic acid, and transesterification of H-phosphinates and H-phosphonates under microwave conditions
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The microwave (MW)-assisted direct esterification of phenyl-H-phosphinic acid, transesterification of the alkyl phenyl-H-phosphinates so obtained, and the similar reaction of dibenzyl phosphite (DBP) were investigated in detail, and the batch accomplishme
- Henyecz, Réka,Keglevich, Gy?rgy,Kiss, Nóra Zsuzsa
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- Nickel-Catalyzed Electrosynthesis of Aryl and Vinyl Phosphinates
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A mild and useful nickel-catalyzed electrochemical phosphonylation of aryl and vinyl bromides is described. We show that alkyl H-phenylphosphinates can be coupled electrochemically with functionalized aryl and vinyl bromides using very simple conditions (Fe/Ni anode, bench-stable nickel pre-catalyst, undivided cell, galvanostatic electrolysis) to furnish the corresponding aryl and vinyl phosphinates in satisfactory to good yields. Couplings can also be applied to heteroaromatic bromides with some limitations like increased propensity to hydro-dehalogenation.
- Daili, Farah,Ouarti, Abdelhakim,Pinaud, Marine,Kribii, Ibtihal,Sengmany, Stéphane,Le Gall, Erwan,Léonel, Eric
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supporting information
p. 3452 - 3455
(2020/05/25)
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- Water determines the products: An unexpected Br?nsted acid-catalyzed PO-R cleavage of P(iii) esters selectively producing P(O)-H and P(O)-R compounds
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Water is found able to determine the selectivity of Br?nsted acid-catalyzed C-O cleavage reactions of trialkyl phosphites: with water, the reaction quickly takes place at room temperature to afford quantitative yields of H-phosphonates; without water, the reaction selectively affords alkylphosphonates in high yields, providing a novel halide-free alternative to the famous Michaelis-Arbuzov reaction. This method is general as it can be readily extended to phosphonites and phosphinites and a large scale reaction with much lower loading of the catalyst, enabling a simple, efficient, and practical preparation of the corresponding organophosphorus compounds. Experimental findings in control reactions and substrate extension as well as preliminary theoretical calculation of the possible transition states all suggest that the monomolecular mechanism is preferred.
- Li, Chunya,Wang, Qi,Zhang, Jian-Qiu,Ye, Jingjing,Xie, Ju,Xu, Qing,Han, Li-Biao
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supporting information
p. 2916 - 2922
(2019/06/18)
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- Phosphinic Acid Based Linkers: Building Blocks in Metal–Organic Framework Chemistry
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Metal–organic frameworks (MOFs) are a chemically and topologically diverse family of materials composed of inorganic nodes and organic linkers bound together by coordination bonds. Presented here are two significant innovations in this field. The first is
- Hynek, Jan,Brázda, Petr,Rohlí?ek, Jan,Londesborough, Michael G. S.,Demel, Jan
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supporting information
p. 5016 - 5019
(2018/03/27)
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- Selective P?C(sp3) Bond Cleavage and Radical Alkynylation of α-Phosphorus Alcohols by Photoredox Catalysis
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Herein the first P?C(sp3) bond cleavage and radical alkynylation of α-phosphorus alcohols to construct phosphonoalkynes is reported. The phosphorus radical is generated upon P?C bond cleavage reaction via the alkoxyl radical through photoredox catalysis with cyclic iodine(III) reagents. Various arylphosphinoyl-, alkylphosphinoyl-, phosphonate-, and phosphonic amide alcohols serve as radical phosphorus precursors to construct phosphonoalkynes for the first time.
- Jia, Kunfang,Li, Junzhao,Chen, Yiyun
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supporting information
p. 3174 - 3177
(2018/02/09)
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- Phosphinatophenylporphyrins tailored for high photodynamic efficacy
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The development of effective photosensitizers is particularly attractive for photodynamic therapy of cancer. Three novel porphyrin photosensitizers functionalized with phosphinic groups were synthesized and their physicochemical, photophysical, and photob
- Hynek, Jan,Konco?ová, Martina,Zelenka, Jaroslav,K?í?ová, Ivana,Ruml, Tomá?,Kubát, Pavel,Demel, Jan,Lang, Kamil
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p. 7274 - 7281
(2018/10/24)
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- New method for synthesizing substituted phosphinate
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The invention discloses a new method for synthesizing substituted phosphinate. The method comprises the step of generating the substituted phosphinate by reducing halogenated phosphonate under the effect of a reducing agent. The optimal preparation method for the substituted phosphinate is screened through a large number of experiments according to the invention; the whole process is reasonably designed; the technological operation is simple and efficient; especially, the optimal reaction conditions are screened, including reaction solvent, reaction temperature, reaction time and optimal reaction pH value; the reaction yield is obviously increased; the yield reaches up to 85-95%; the side reaction is less; the production cost is greatly lowered; the industrial production can be realized; and the method has a wide application prospect.
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Paragraph 0032; 0037-0038
(2017/12/27)
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- Convenient synthesis of allenylphosphoryl compounds: Via Cu-catalysed couplings of P(O)H compounds with propargyl acetates
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A novel Cu-catalysed substitution reaction of propargyl acetates with P(O)H compounds is developed to afford allenylphosphoryl compounds via C-P bond coupling in high yields under mild conditions. A plausible mechanism involving the nucleophilic interception of the Cu-allenylidene intermediates is proposed.
- Shen, Ruwei,Luo, Bing,Yang, Jianlin,Zhang, Lixiong,Han, Li-Biao
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supporting information
p. 6451 - 6454
(2016/05/24)
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- T3P-assisted esterification and amidation of phosphinic acids
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A few phosphinic acids, such as phenylphosphinic acids, 1-hydroxy-3-phospholene 1-oxides and 1-hydroxyphospholane oxides are esterified with simple alcohols in the presence of propylphosphonic anhydride (T3P). If 1.1 equiv of the T3P reagent is used, the esterifications are fast and efficient at 25° C. In the case of more reactive models it was enough to apply 0.66 equiv of T3P at 85°C under microwave conditions. The amidation of 1-hydroxy-3-methyl-3-phospholene oxide could also be accomplished under similar conditions.
- Jablonkai, Erzsébet,Henyecz, Réka,Milen, Mátyás,Kóti, János,Keglevich, Gy?rgy
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p. 8280 - 8285
(2015/03/05)
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- Phosphonothioate hydrolysis by molybdocene dichlorides: Importance of metal interaction with the sulfur of the thiolate leaving group
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The metallocene bis(cyclopentadienyl)molybdenum(IV) dichloride Cp 2MoCl2 hydrolyzes O,S-diethyl phenylphosphonothioate (1) with only P-S scission to yield a phosphonate under mild aqueous conditions. In terms of degrading phosphonoth
- Kuo, Louis Y.,Baker, Devon C.,Dortignacq, Adria K.,Dill, Kristina M.
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p. 4759 - 4765
(2013/09/24)
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- Synthesis of 2-pyridylphosphinate and thiophosphinate derivatives by nucleophilic aromatic substitution of N-methoxypyridinium tosylates
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We developed a straightforward and cost-effective method for the synthesis of 2-pyridylphosphinate derivatives based on a nucleophilic aromatic substitution of N-methoxypyridinium salts. The method proved to be useful for synthesizing various 2-pyridylphosphinates and thiophosphinates, including an optically active compound, from H-phosphinate precursors.
- Oka, Natsuhisa,Ito, Kousuke,Tomita, Futoshi,Ando, Kaori
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supporting information
p. 1630 - 1632
(2013/02/23)
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- Stereochemical inversion of phosphonothioate methanolysis by La(III) and Zn(II): Mechanistic implications for the degradation of organophosphate neurotoxins
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The utility of phosphonothioate methanolysis to degrade organophosphate neurotoxins has prompted the stereochemical investigation of this useful transformation. The methanolysis of enantiomerically pure O,S-diethyl phenylphosphonothioate (5) was studied b
- Kuo, Louis Y.,Glazier, Sara K.
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experimental part
p. 328 - 335
(2012/03/12)
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- Synthesis of phosphonamidate peptides by Staudinger reactions of silylated phosphinic acids and esters
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The Staudinger reaction of unprotected azido-peptides with silylated phosphinic acids and esters on the solid support offers a straightforward acid-free entry to different phosphonamidate peptide esters or acids under mild conditions in high purity and yield.
- Wilkening, Ina,Signore, Giuseppe Del,Hackenberger, Christian P. R.
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supporting information; experimental part
p. 349 - 351
(2011/03/17)
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- NEW PHOSPHORUS CONTAINING HETEROCYCLIC COMPOUNDS, SUGAR ANALOGUES, AND COMPOSITIONS HAVING ANTI-CANCER ACTIVITY CONTAINING THE SAME
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The invention provides new anticancer compounds of formula (1) such as defined in the present description. The invention also provides pharmaceutical compositions to be used in human or veterinary medicine, comprising at least one compound of formula (1). The present invention further relates to a compound of formula (1) such as defined in the present description, for use as a drug. The invention further relates to the use of a compound of formula (1) for manufacturing a human or animal anticancer pharmaceutical composition.
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Page/Page column 25-26
(2009/03/07)
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- Anomalous reaction of ethyl bromofluoro- and difluoro-acetates with dialkylphosphonites
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The Michaelis-Arbuzov reaction of ethyl α-bromo-α-fluoro- and α, α-difluoro-acetates with dialkyl phenylphosphonites leads to the formation of unusual products including a fluorophosphinate. The reaction of ethyl bromofluoracetate with diisopropyl- and dimethyl-phenylphosphonites furnishes a complex mixture of eight and five compounds respectively. Five different compounds are obtained when ethyl bromodifluoroacetate is reacted with diisopropyl phenylphosphonite. Dimethyl phenylphosphonite yields three compounds when heated with bromochloromethane. The probable mechanism of formation of the compounds and their mass spectral characterization using GC-MS, tandem MS-MS and DART techniques are presented in this paper. Copyright Taylor & Francis Group, LLC.
- Durst,Rohrbaugh,Smith,Nilles,Connell,Laramee,Munavalli
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experimental part
p. 2655 - 2668
(2009/09/25)
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- Synthesis of H-phosphinates by the UV light - Mediated fragmentation- related phosphorylation using simple P-heterocycles
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Photolysis of aryl-substituted 2,5-dihydrophosphole oxides (5a-e and 8) in the presence of methanol afforded methyl aryl-H-phosphinates (2a-e) in good yields. In the case of 1-ethyl-, cyclohexyl-, or ethoxy-2,5-dihydrophosphole oxides, the reaction was mu
- Szelke, Helga,Kovacs, Janos,Keglevich, Gyoergy
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p. 2927 - 2934
(2007/10/03)
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- New 7-phosphanorbornenes derived from 2-methyl-1-phenyl- And 1-cyclohexyl-3-methyl-2,5-dihydro-1H-phosphole 1-oxides
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Novel 7-phosphanorbornene derivatives, such as 4, 5, 10, and 11 were synthesized utilizing 1-phenyl-2-methyl-2,5-dihydro-1H-phosphole oxide (1) and 1-cyclohexyl-3-methyl-2,5-dihydro-1H-phosphole oxide (7) as the starting materials. Products 4 and 10 were
- Kovacs, Janos,Szabo, Nora Balazsdi,Nagy, Zoltan,Ludanyi, Krisztina,Keglevich, Gyoergy
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p. 320 - 326
(2007/10/03)
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- Hewitt reaction revisited
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A range of alkyl phenylphosphonites are prepared from the reaction of phenylphosphinic acid with the corresponding alkyl chloroformates. A mechanism for this reaction is proposed.
- Afarinkia, Kamyar,Yu, Hiu-Wan
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p. 781 - 783
(2007/10/03)
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- Synthesis of a novel diarylphosphinic acid: A distorted ground state mimic and transition state analogue for amide hydrolysis
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We describe herein the synthesis of a new unsymmetrical diarylphosphinic acid, a hapten aimed to produce catalytic antibodies for the hydrolysis of heterocyclic amides. The phosphinate functionality was selected as a mimic both of the tetrahedral intermed
- Schuman, Marc,Lopez, Xabier,Karplus, Martin,Gouverneur, Véronique
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p. 10299 - 10307
(2007/10/03)
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- Orthosilicate-mediated esterification of monosubstituted phosphinic acids
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(matrix presented) Monosubstituted phosphinic acids are esterified with orthosilicates in excellent yields. Phosphinylidene-containing acids react selectively under these conditions, while disubstituted phosphinic acids and phosphonic acids remain unchanged. One-pot procedures are also described for the preparation of phosphinate esters from an alcohol. This novel method provides a convenient and general alternative to more commonly employed conditions such as diazomethane or carbodiimide.
- Dumond, Yves R.,Baker, Rhonda L.,Montchamp, Jean-Luc
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p. 3341 - 3344
(2007/10/03)
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- Phosphinic ester substituted benzopyran derivatives
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STR1 and pharmaceutically acceptable salts thereof wherein Y is a single bond, --CH 2 --, --C(O)--, --S-- or --N(R 11)--; and R 1 to R 6 are as defined herein. These compounds have potassium channel activating activity and are useful, therefore for example, as cardiovascular agents.
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- Experiments on the Generation of 2-Coordinate Phosphoryl Species by Fragmentation of 7-Phosphanorbornene and 3-Phospholene Derivatives
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2,6-Di-tert-butyl-4-methylphenyl phosphenite (ArOP=O) was released into the gas phase on heating a neat sample of a 7-phosphanorbornene derivative 6 bearing this aryloxy substituent at 300 deg C (0.01 mm).Attempts to prepare 1-adamantyl phosphenite simila
- Quin, Louis D.,Jankowski, Stefan,Rudzinski, Juliusz,Sommese, Anthony G.,Wu, Xiao-Ping
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p. 6212 - 6216
(2007/10/02)
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- Palladium catalyzed preparation of monoaryl and diarylphosphinates from methyl phosphinate
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A simple and effective preparation of methyl esters of monoarylphosphinic acids has been developed, which involves palladium catalyzed coupling of aryl iodides with methyl phosphinate in the presence of tertiary amines or propylene oxide (1,2-epoxypropane
- Lei,Stoakes,Schwabacher
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p. 1255 - 1260
(2007/10/02)
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- Phenylfluorophosphoranes: axial-equatorial fluorine exchange in RC6H4PF3H and intermolecular exchange in the PhPF2(H)OMe-MeOH-base system
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Activation parameters for axial-equatorial fluorine exchange in arylfluorophophoranes PC6H4PF3H, where R = o-CF3, m-CF3, m-CH3, were studied by the dynamic nmr technique. Δ G298(excit.) varied between 53 and 56 kJ mol-1.The synthesis of difluoromethoxyphenylphosphorane, PhPF2(H)OMe, from PhPF2 and MeOH is catalyzed by small amounts of Et3N, pyridine, PhPF3H, or HF.Rapid intermolecular ligand exchange occurs in PhPF2(H)OMe after addition of methanol and a base such as triethylamine or pyridine.Under these conditions, exchange of fluorine, hydrogen, and methoxy ligands occurs, as shown by 1H, 19F, and 31P nmr.From a line shape analysis of the 31P nmr spectrum, the rate of P-F cleavage was found to be first order (1.17 +/- 0.2) in Et3N concentration, with Δ G(excit.)298 = 50 kJ mol-1 and Δ S (excit.) = -67 J mol-1 deg-1.An equilibrium constant of 1.8 at 25 deg C was found for the reaction of PhPF2(H)OMe with PhPF2.
- Kruczynski, Leonard J.,Lemire, Alberta E.,Marat, Kirk,Janzen, Alexander F.
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p. 488 - 491
(2007/10/02)
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- Kinetic Facial Selectivity in Nucleophilic Displacements at Tetracoordinate Phosphorus: Kinetics and Stereochemistry in the Reaction of Sodium Ethoxide with O,S-Dimethyl Phenylphosphonothioate
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The reaction of ethoxide ion with O,S-dimethyl phenylphosphonothioate (1a) proceeds with competitive displacements of the methylthio and methoxy ligands.Each displacement occurs with complete inversion of configuration.The two products, ethyl methyl pheny
- DeBruin, Kenneth E.,Tang, Chen-lan W.,Johnson, David M.,Wilde, Ronnie L.
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p. 5871 - 5879
(2007/10/02)
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- PHOTOCHEMICAL REACTIONS OF PHOSPHAALKENES
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Photolysis of phosphaalkenes leads to an inversion of polarity of the phosphorus carbon double bond and to a cleavage into transient phosphinidene and carbene; unexpected alcoholysis of a PIII-C bond and the cycloaddition of a linear phosphaalkene on a diene are also reported.
- Meriem, Abdelkader,Majoral, Jean-Pierre,Revel, Monique,Navech, Jacques
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p. 1975 - 1978
(2007/10/02)
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- SYNTHESIS AND PHOTOCHEMICAL REACTION OF DIELS-ALDER ADDUCT OF PHOSPHOLE OXIDE AND CYCLOPENTADIENE
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Irradiation of 1-phenylphosphole oxide-cyclopentadiene adduct gave a caged product, whereas similar irradiation of 1,2,5-triphenylphosphole oxide-cyclopentadiene adduct afforded a cleavaged product.
- Tomioka, Hideo,Miura, Shinichi,Izawa, Yasuji
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p. 3353 - 3356
(2007/10/02)
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