- Copper-Catalyzed Microwave-Expedited Oxyphosphorylation of Alkynes with Diethyl Phosphite and t-Butyl Hydroperoxide Synthesis of Densely Functionalized Phosphonylated Indenones
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Treatment of alkynes with diethyl phosphite and t-butyl hydroperoxide in the presence of [Cu(MeCN)4]BF4 under microwave irradiation produced the oxyphosphorylation of the triple bond, giving rise to the corresponding β-ketophosphonates in moderate-to-good yields. When the triple bond was conjugated to a carbonyl group bearing an aromatic ring, it led to the cyclization of the resulting ketone intermediate, producing eventually different phosphonylated indenones.
- Maciás-Benítez, Pablo,Sierra-Padilla, Alfonso,Tenorio, Manuel J.,Moreno-Dorado, F. Javier,Guerra, Francisco M.
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p. 16409 - 16424
(2021/11/16)
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- Access to chiral α-substituted-β-hydroxy arylphosphonates enabled by biocatalytic dynamic reductive kinetic resolution
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Ketoreductase (KRED)-catalyzed dynamic reductive kinetic resolution (DYRKR) of α-substituted-β-keto arylphosphonates was developed as a generic and stereoselective approach to synthesize chiral α-substituted-β-hydroxy arylphosphonates, with moderate-to-excellent isolated yield (up to 96%), good-to-excellent diastereoselectivity (up to >99 : 99% ee) being achieved.
- Chen, Fener,Huang, Zedu,Li, Zihan,Tao, Yuan,Wang, Zexu,Wu, Xiaofan,Yu, Xiaomin,Zeng, Yiping
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supporting information
p. 2672 - 2677
(2020/04/17)
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- Copper ferrite nanoparticles catalyzed formation of β-Ketophosphonates via oxyphosphorylation of styrenes with H-phosphonates: A DFT study on UV–vis absorption spectra
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Typical copper ferrite nanoparticles (CuFe2O4) were used as a catalyst for one-pot synthesis of β-ketophosphonates via the reaction of alkenes with H-phosphonates under conventional heating conditions. The catalyst was prepared by using the coprecipitation method and was analyzed by physiochemical techniques. By using this catalyst system, several types of useful and new β-ketophosphonate products were obtained in very good to excellent yields under optimized reaction conditions in a novel way. Furthermore, the catalyst is recyclable and reusable from the reaction.
- Azaryan, Reza,Daneshfar, Maryam,Moghaddam, Firouz Matloubi,Pirat, Jean-Luc
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- Bivalent copper complex containing diphosphine ortho-position carborane ligand, preparation method and application thereof
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The invention relates to a bivalent copper complex containing a diphosphine ortho-position carborane ligand, a preparation method and application thereof. The copper complex is prepared by the following method of: adding an n-BuLi solution dropwise into an ortho-position carborane o-C2B10H12 solution, and carrying out stirring reaction, then adding halogenated phosphine for continuous reaction, adding copper acetate Cu(OAc)2 into the reaction system for continuous reaction, after the reaction is finished, performing separating to obtain the diphosphine ortho-position carborane ligand, and applying the copper complex to catalytic synthesis of a beta-carbonyl phosphine oxide compound. Compared with the prior art, the synthesis process has excellent selectivity and high yield, the copper complex can catalyze alpha-haloketone and phosphite to react to synthesize the beta-carbonyl phosphine oxide compound under the room temperature condition, and the reaction is efficient, green and environmentally friendly.
- -
-
Paragraph 0029; 0033-0036; 0037
(2020/09/16)
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- Mukaiyama reagent-promoted metal-free preparation of alkynyl sulfones and phosphonates under mild conditions
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An efficient and mild route for the formation sulfur or phosphor-substituted alkynes was herein demonstrated. The Mukaiyama reagent-mediated transformation started from easily-accessible substrates without carbon-carbon triple bonds, and the reaction proceeded under mild conditions (room temperature) in a one-pot manner, requiring for no transition metal-catalysts. The practical protocol featured for good functional groups tolerance (up to 41 examples) and high efficiency (up to 91% yields) towards alkynyl sulfones and alkynyl phosphonates at low cost.
- Qi, Danyang,Dong, Wanrong,Peng, Zhihong,Zhang, Yingjun,An
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- Manganese-catalyzed oxophosphorylation reaction of carbon–carbon double bonds using molecular oxygen in air
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A novel aerobic manganese-catalyzed oxophosphorylation reaction of carbon–carbon double bonds of styrene derivatives and vinyl ethers using diethyl H-phosphonates was developed. This direct transformation of alkenes to β-ketophosphonate readily proceeded at room temperature via the direct incorporation of molecular oxygen present in air (open flask).
- Yamamoto, Daisuke,Ansai, Hiromasa,Hoshino, Junichi,Makino, Kazuishi
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p. 873 - 879
(2018/09/10)
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- Mn(OAc)3-Promoted Oxidative Csp3-P Bond Formation through Csp2-Csp2 and P-H Bond Cleavage: Access to β-Ketophosphonates
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The Mn(OAc)3-promoted oxidative phosphonylation of N,N-dimethylenaminones with H-phosphonates, involving a chemo- and regioselective Csp2-Csp2 bond cleavage and Csp3-P bond formation in one step, provided successfully functionalized β-ketophosphonates under mild reaction conditions. Oxidative Csp3-H/P-H cross-coupling reactions via Csp3-C(C=O) bond cleavage and mechanistic studies are conducted preliminarily, and a possible mechanism is proposed. This novel method proceeds in good to excellent yields, shows operational simplicity, broad substrate scope, and large-scale preparation.
- Zhou, Pan,Hu, Biao,Li, Lingdan,Rao, Kairui,Yang, Jiao,Yu, Fuchao
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p. 13268 - 13276
(2017/12/26)
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- Silver-Catalyzed Oxidative C(sp3)?P Bond Formation through C?C and P?H Bond Cleavage
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The silver-catalyzed oxidative C(sp3)?H/P?H cross-coupling of 1,3-dicarbonyl compounds with H-phosphonates, followed by a chemo- and regioselective C(sp3)?C(CO) bond-cleavage step, provided heavily functionalized β-ketophosphonates. This novel method based on a readily available reaction system exhibits wide scope, high functional-group tolerance, and exclusive selectivity.
- Li, Lili,Huang, Wenbin,Chen, Lijin,Dong, Jiaxing,Ma, Xuebing,Peng, Yungui
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supporting information
p. 10539 - 10544
(2017/08/22)
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- MnIII-catalyzed phosphorylation of vinyl azides: The synthesis of β-keto phosphine oxides
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MnIII-catalyzed functionalization of vinyl azides via phosphorylation was developed to synthesize various β-keto phosphine oxides in high yields. The transformation is operated in mild conditions and tolerant of a range of functional groups. Control reaction indicates that the reaction mechanism might proceed via the generation of a phosphonated iminyl radical intermediate.
- Tang, Pai,Zhang, Can,Chen, En,Chen, Binhui,Chen, Wenteng,Yu, Yongping
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supporting information
p. 2157 - 2161
(2017/05/09)
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- Cu(i)/Fe(III)-Catalyzed C-P cross-coupling of styrenes with H-phosphine oxides: A facile and selective synthesis of alkenylphosphine oxides and β-ketophosphonates
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Cu(i)/Fe(iii)-Catalyzed phosphorylation and oxyphosphorylation of styrenes with H-phosphonates which can be controlled by varying the reaction temperature are developed. This study offers a new and expedient strategy for the synthesis of useful alkenylphosphine oxides and β-ketophosphonates in satisfactory yields. Moreover, the transformation is proposed to proceed via a radical process and exhibits a broad substrate scope and good functional group tolerance.
- Gu, Jian,Cai, Chun
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supporting information
p. 4226 - 4230
(2017/07/10)
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- Mn(OAc)3-Mediated Synthesis of 3-Phosphonyldihydrofurans from β-Ketophosphonates and Alkenes
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A new, general method for the synthesis of 3-phosphonyldihydrofuran derivatives has been achieved through Mn(OAc)3-mediated radical cyclization between β-ketophosphonates and alkenes. This transformation allows the direct formation of C-C/C-O bonds and the construction of a dihydrofuran ring in one reaction with operational simplicity and excellent functional-group compatibility.
- Lu, Guozhang,Lin, Binzhou,Gao, Yuzhen,Ying, Jianxi,Tang, Guo,Zhao, Yufen
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p. 724 - 728
(2017/03/21)
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- A process for preparing β - carbonyl phosphine ester method
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The invention discloses a method for synthesizing beta-carboxyl phosphate from alkyne or alkynyl carboxylic compounds and phosphite ester in the presence of copper/iron salt serving as catalysts and molecular oxygen serving as an oxidant. According to the method, multifunctional beta-carboxyl phosphate is obtained by virtue of a novel method having wide substrate range in the presence of the inexpensive catalysts (copper salts and iron salts) in oxygen, which is in a sharp contrast with previously reported view that alkyne cannot act in the presence of molecular oxygen. The method disclosed by the invention has the advantages of mild reaction conditions, easily available raw materials, good compatibility with various reactants, strong practicality and high yield and can be widely applied to various functional reactions.
- -
-
Paragraph 0074; 0075; 0076
(2017/07/31)
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- Substituent-Controlled Chemoselective Cleavage of C = C or Csp2 - C(CO) Bond in α,β-Unsaturated Carbonyl Compounds with H-Phosphonates Leading to β-Ketophosphonates
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An unprecedented substituent-controlled chemoselective cleavage of C = C double bond or C(sp2)-C(CO) bond along with aerobic phosphorylation of α,β-unsaturated carbonyl compounds with H-phosphonates through a radical process has been disclosed. The current strategy provides an access to β-ketophosphonates under mild conditions with a wide substrate scope.
- Zhou, Yao,Rao, Changqing,Mai, Shaoyu,Song, Qiuling
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p. 2027 - 2034
(2016/03/15)
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- Synthesis of α-trifluoromethyl-β-keto phosphonates by electrophilic trifluoromethylation with Togni reagent
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A new synthetic method of trifluoromethylated phosphonates was developed via electrophilic trifluoromethylation with Togni reagent. A variety of β-keto phosphonates were converted into the corresponding α-trifluoromethyl-β-keto phosphonates in moderate to good yields. This protocol could also be extended to other fluoroalkylation reactions, such as pentafluoroethylation.
- Fu, Wen-Zhi,Huang, Yangen,Xu, Xiu-Hua,Qing, Feng-Ling
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supporting information
p. 415 - 420
(2016/04/05)
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- Addressing the Glycine-Rich Loop of Protein Kinases by a Multi-Facetted Interaction Network: Inhibition of PKA and a PKB Mimic
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Protein kinases continue to be hot targets in drug discovery research, as they are involved in many essential cellular processes and their deregulation can lead to a variety of diseases. A series of 32 enantiomerically pure inhibitors was synthesized and tested towards protein kinase A (PKA) and protein kinase B mimic PKAB3 (PKA triple mutant). The ligands bind to the hinge region, ribose pocket, and glycine-rich loop at the ATP site. Biological assays showed high potency against PKA, with Ki values in the low nanomolar range. The investigation demonstrates the significance of targeting the often neglected glycine-rich loop for gaining high binding potency. X-ray co-crystal structures revealed a multi-facetted network of ligand-loop interactions for the tightest binders, involving orthogonal dipolar contacts, sulfur and other dispersive contacts, amide-π stacking, and H-bonding to organofluorine, besides efficient water replacement. The network was analyzed in a computational approach.
- Lauber, Birgit S.,Hardegger, Leo A.,Asraful, Alam K.,Lund, Bjarte A.,Dumele, Oliver,Harder, Michael,Kuhn, Bernd,Engh, Richard A.,Diederich, Fran?ois
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supporting information
p. 211 - 221
(2016/01/25)
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- Preparation method of beta-ketone substituted phosphate ester compound
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The invention provides a preparation method of a beta-ketone substituted phosphate ester compound. The beta-ketone substituted phosphate ester compound is generated through a reaction of initial materials comprising alkenyl azide and phosphite ester in an organic solvent with manganese acetate as an oxidant. The preparation method has the advantages of reasonable design, easily available raw materials, mild reaction conditions, no high temperature reflow, high safety and convenience, and high yield, and allows the yield of most of products to be 70% or above. The preparation method is a method for constructing the beta-ketone substituted phosphate ester compound and having the advantages of simple operation, fastness, mildness and diversification; and the two initial raw materials are obtained through a one-step technology, so reaction raw materials are cheap and can be easily obtained. The general formula (I) of the beta-ketone substituted phosphate ester compound is shown in the description.
- -
-
Paragraph 0032-0036; 0049-0052
(2019/08/28)
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- Palladium-Catalyzed Oxidative Cyclization for the Synthesis of Indolyl/Pyrrolyl 3-Phosphonates
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Imino-/enaminophosphonates derived from amines and diethyl phenacyl phosphonates undergo oxidative cyclization via C H bond activation catalyzed by palladium chloride to provide a convenient route for the synthesis of substituted indol-3-yl and pyrrol-3-yl phosphonates. (Figure presented.) .
- Mishra, Aniket,Deb, Indubhusan
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p. 2267 - 2272
(2016/07/29)
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- β-Ketophosphonates formation via deesterification or deamidation of cinnamyl/alkynyl carboxylates or amides with H-phosphonates
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We report here an unprecedented Fe/Cu synergistically catalyzed deesterificative or deamidative oxyphosphorylation of unsaturated carboxylates or amides with H-phosphonates. The valuable β-ketophosphonates were obtained along with chemoselective cleavage of Csp2-C(CO) or Csp-C(CO) bonds in good yields under oxygen atmosphere with a wide substrate scope.
- Zhou, Yao,Zhou, Mingxin,Chen, Ming,Su, Jihu,Du, Jiangfeng,Song, Qiuling
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p. 103977 - 103981
(2015/12/24)
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- Base-induced one-pot preparation of N- or P-substituted alkynes
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An efficient method for the formation of C(sp)-N or C(sp)-P bonds is described. The facile transformation proceeds under mild conditions (0 or -20 °C) in a one-pot manner, and does not require transition-metal catalysts. The base-induced protocol exhibits good functional group tolerance (up to 44 examples) and high efficiency (up to 94 % yield) towards rare heteroatom-substituted acetylenes (N or P). Furthermore, the proposed mechanism was supported by the isolation of a key intermediate. An efficient method for the formation of C(sp)-N or C(sp)-P bonds is described. The facile transformation proceeds in the absence of any transition-metal catalysts under mild conditions (0 or -20 °C) in a one-pot manner with good functional group compatibility and with high efficiency.
- Zhang, Yang,Zhang, Yanqin,Xiao, Jing,Peng, Zhihong,Dong, Wanrong,An, Delie
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supporting information
p. 7806 - 7815
(2015/12/31)
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- Cu/Fe-Cocatalyzed Formation of β-Ketophosphonates by a Domino Knoevenagel-Decarboxylation-Oxyphosphorylation Sequence from Aromatic Aldehydes and H-Phosphonates
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A domino Knoevenagel-decarboxylation-alkene difunctionalization sequence has been developed for the conversion of benzaldehydes into β-ketophosphonates, catalyzed by a cooperative Cu/Fe system, whereby CP and CO bonds are formed simultaneously in a one-pot reaction. The reaction proceeds in good yields and with a broad substrate scope and environmentally benign conditions.
- Zhou, Mingxin,Zhou, Yao,Song, Qiuling
-
supporting information
p. 10654 - 10658
(2015/07/20)
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- β-Ketophosphonate formation via aerobic oxyphosphorylation of alkynes or alkynyl carboxylic acids with H-phosphonates
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A synergistic Cu/Fe-catalyzed aerobic oxyphosphorylation of alkynes or alkynyl carboxylic acids with H-phosphonate is disclosed. The useful β-ketophosphonate products were obtained in good yields under oxygen atmosphere in a novel way. This reaction exhibits a wide substrate scope, and the mechanistic experiments indicate that a radical mechanism forms both C-P and C=O bonds simultaneously. This mechanism contrasts existing aerobic difunctionalization of alkynes.
- Zhou, Mingxin,Chen, Ming,Zhou, Yao,Yang, Kai,Su, Jihu,Du, Jiangfeng,Song, Qiuling
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supporting information
p. 1786 - 1789
(2015/04/14)
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- Copper/Iron-Catalyzed Aerobic Oxyphosphorylation of Terminal Alkynes Leading to β-Ketophosphonates
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A copper/iron-catalyzed oxyphosphorylation of alkynes with H-phosphonates through a radical process was developed. The present protocol provides an attractive approach to β-ketophosphonates in moderate to good yields, with the advantages of readily available substrate, high functional group tolerance and operation simplicity. (Chemical Equation Presented).
- Yi, Niannian,Wang, Ruijia,Zou, Huaxu,He, Weibao,Fu, Wenqiang,He, Weimin
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p. 5023 - 5029
(2015/05/27)
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- Synthetic entry into 1-phosphono-3-azabicyclo[3.1.0]hexanes
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3-Azabicyclo[3.1.0]hex-2-en-1-yl phosphonates were prepared in a five-step reaction route from β-ketophosphonates. The key steps in this sequence are an atom-transfer radical cyclization and an unforeseen lithium-halogen exchange with n-BuLi. The cyclization reaction proceeds with excellent diastereoselectivity. The resulting cyclic imines were reduced, and 3-azabicyclo[3.1.0]hexan-1-yl phosphonates were obtained.
- Debrouwer, Wouter,Heugebaert, Thomas S. A.,Van Hecke, Kristof,Stevens, Christian V.
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p. 8232 - 8241
(2013/09/24)
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- Acylation of diethyl phosphonoacetic acid via the MgCl2/Et3N system: A practical synthesis of β-keto phosphonates
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A one pot simple procedure for the synthesis of β-keto phosphonates has been developed using the MgCl2/Et3N base system to generate the magnesium enolate of diethyl phosphonoacetic acid. This intermediate reacts with acid chlorides or imidazolides to give, after workup, the title compounds in good yields.
- Corbel, Bernard,L'Hostis-Kervella, Isabelle,Haelters, Jean-Pierre
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p. 609 - 618
(2007/10/03)
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- Acylation of in situ generated trimethylsilyl diethylphosphonoacetate using magnesium chloride-triethylamine: a practical synthesis of β-keto phosphonates
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In situ generated trimethylsilyl diethylphosphonoacetate from diethyl phosphonoacetic acid can be acylated with carboxylic acid chlorides in the presence of magnesium chloride to prepare a variety of β-keto phosphonates.This synthetic methods is suitable for the preparation of β-keto phosphonates in the laboratory and also for large-scale production.
- Kim, Dae Young,Kong, Myeon Sik,Lee, Kilsung
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p. 1360 - 1364
(2007/10/03)
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- A practical synthesis of β-keto phosphonates from triethyl phosphonoacetate
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An efficient and practical preparation of β-keto phosphonates, via acylation reaction of triethyl phosphonoacetate with carboxylic acid chlorides in the presence of magnesium chloride-triethylamine followed by decarbethoxylation, is described.
- Kim, Dae Young,Kong, Myeon Sik,Kim, Taek Hyeon
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p. 2487 - 2496
(2007/10/03)
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- On a safe and practical method for the preparation of β-keto phosphonates
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Acylations of the magnesium enolate derivatives of trimethyl and triethylphosphonoacetates, using a magnesium chloride-triethylamine system, lead to 2-acetylphosphonoacetates which are decarbalkoxylated to give β-keto phosphonates.
- Corbel, Bernard,L'Hostis-Kervella, Isabelle,Haelters, Jean-Pierre
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p. 2561 - 2568
(2007/10/03)
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- STUDIES ON ORGANOPHOSPHORUS COMPOUNDS. 87. A CONVENIENT PROCEDURE FOR THE PREPARATION OF DIETHYL 2-OXOALKYLPHOSPHONATES
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A facile one-pot procedure for the synthesis of diethyl 2-oxoalkylphosphonates is described.It involves an Arbuzov rearrangement of triethylphosphite with 1-bromoketone in which the carbonyl function was masked in the form of benzenesulfonyl hydrazone.Subsequent deprotection via oxidative cleavage affords the title compounds with fair yields.Key words: 2-Ketoalkylphosphonates, Arbuzov rearrangement, carbonyl protection.
- Yuan, Chengye,Xie, Rongyuan
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- An Efficient Synthesis of Dialkyl 2-Oxoalkanephosphonates and Diphenyl-2-oxoalkylphosphine Oxides from 1-Chloralkyl Ketones
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The synthesis of dialkyl 2-oxoalkanephosphonates and diphenyl-2-oxoalkylphosphine oxides, via an Arbuzov reaction of trialkyl phosphites or ethoxydiphenylphosphine with methoxycarbonylhydrazono derivatives of 1-chloroalkyl ketones followed by carbonyl deprotection, is described.
- Corbel, Bernard,Medinger, Luc,Haelters, Jean Pierre,Sturtz, Georges
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p. 1048 - 1051
(2007/10/02)
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