1067-71-6Relevant articles and documents
Addition of secondary amines to alkynephosphonates
Panarina,Dogadina,Ionin
, p. 1729 - 1737 (2003)
Addition of secondary amines to diethyl alkynephosphonates, catalyzed by Cu(I) salts, proceeds regio- and stereospecifically and yields diethyl (E)-2-diethylaminooalkenephosphonates. The E configuration was established by analysis of the vicinal coupling constants between the phosphorus and carbon nuclei in the 13C NMR spectra of the reaction products and model compounds: 3JPC is 6-10 Hz at the cis arrangement of the coupled nuclei and 16 Hz or higher at the trans arrangement. In all the diethyl diethylaminoalkenephosphonates obtained, 3JPC is about 5 Hz, suggesting cis addition.
A new synthesis of β-keto phosphonate from aryl epoxysulfones and dialkyl hydrogen phosphite
Koh, Young Joo,Oh, Dong Yung
, p. 2147 - 2148 (1993)
Reaction of α-subtituted arylsulfonyl epoxide with diethyl phosphite sodium salt gave β-keto phosphonate in good yield.
Savignac,Mathey
, p. 2829 (1976)
Synthesis of diethyl 2-thioxo-1,2,3,4-tetrahydroand hexahydropyrimidine-5-phosphonates
Fesenko, Anastasia A.,Cheshkov, Dmitrii A.,Shutalev, Anatoly D.
, p. 51 - 53 (2008)
The reaction of sodium enolate of diethyl (2-oxoprop-1-yl)phosphonate with N-(1-tosylprop-1-yl)thiourea results in the stereoselective formation of diethyl (4R*,5R*,6R*)-6-ethyl-4-hydroxy-4-methyl-2-thioxohexahydropyrimidine-5-phosphonate, which is transformed into diethyl 4-ethyl-6-methyl-2-thioxo-1,2,3,4-tetrahydropyrimidine-5-phosphonate and diethyl (4R*,5S*,6R*)-4-ethyl-6-methyl-2-thioxohexahydropyrimidine-5-phosphonate by acid-catalysed dehydration and stereoselective reduction with NaBH4-CF3COOH, respectively.
REGIOCONTROLLED METALATION OF DIETYHL β-DIALKYLAMINOVINYLPHOSPHONATES: A NEW SYNTHESIS OF SUBSTITUTED β-KETOPHOSPHNATES
Boeckman, Robert K.,Walters, Michael A.,Koyano, Hiroshi
, p. 4787 - 4790 (1989)
The metalation of diethyl β-dialkylaminovinylphosphonates (vinylogous phosphoramides (VPA)) and their reaction with a variety of electrophiles is described.Upon mild hydrolysis these derivatives provide good yields of β-ketophosphonates.
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Tomioka,H. et al.
, p. 1501 - 1506 (1969)
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Biocatalytic syntheses of chiral non-racemic 2-hydroxyalkanephosphonates
Zurawinski, Remigiusz,Nakamura, Kaoru,Drabowicz, Jozef,Kielbasinski, Piotr,Mikolajczyk, Marian
, p. 3139 - 3145 (2001)
A series of 2-oxoalkanephosphonates 2 were screened for reduction with Geotrichum candidum. Only diethyl 2-oxopropanephosphonate 2a underwent asymmetric reduction to give (+)-(R)-diethyl 2-hydroxypropanephosphonate 3a with 98% e.e. In turn, a series of racemic 2-hydroxyalkanephosphonates 3 were acetylated under kinetic resolution conditions in the presence of various lipases to give the corresponding 2-acetoxyalkanephosphonates 4 and recovered alcohols 3 in good yields and with e.e. up to 93%.
Reactivity of [60]Fullerene with primary nitro compounds: Addition or catalysed condensation to isoxazolo[60]fullerenes
Biagiotti, Giacomo,Cicchi, Stefano,De Sarlo, Francesco,Machetti, Fabrizio
, p. 7906 - 7915 (2014)
The catalysed condensation of [60]fullerene with ethyl nitroacetate (1b) or analogous activated nitro derivatives to afford isoxazolino[60]fullerenes has been achieved in both homogeneous and heterogeneous conditions. This direct synthetic approach is more convenient than previous methods. Model reactions with electron-poor dipolarophiles led to either condensation to isoxazolines or to conjugate addition products, depending on the nitro compound and catalyst. The former product was favoured by the use of CuII in the catalytic system. Conversely, [60]fullerene underwent catalytic condensation, even in the absence of copper(II) salts, only with activated nitro compounds and addition only with nitroalkanes in excess base. Note, the formal conjugated fullerene addition product was obtained in isomeric form, as previously reported. A possible explanation is presented for this contrasting behaviour.
Acylation of diethyl phosphonoacetic acid via the MgCl2/Et3N system: A practical synthesis of β-keto phosphonates
Corbel, Bernard,L'Hostis-Kervella, Isabelle,Haelters, Jean-Pierre
, p. 609 - 618 (2000)
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.
Enhanced Solubilization of Class B Radical S-Adenosylmethionine Methylases by Improved Cobalamin Uptake in Escherichia coli
Lanz, Nicholas D.,Blaszczyk, Anthony J.,McCarthy, Erin L.,Wang, Bo,Wang, Roy X.,Jones, Brianne S.,Booker, Squire J.
, p. 1475 - 1490 (2018)
The methylation of unactivated carbon and phosphorus centers is a burgeoning area of biological chemistry, especially given that such reactions constitute key steps in the biosynthesis of numerous enzyme cofactors, antibiotics, and other natural products of clinical value. These kinetically challenging reactions are catalyzed exclusively by enzymes in the radical S-adenosylmethionine (SAM) superfamily and have been grouped into four classes (A-D). Class B radical SAM (RS) methylases require a cobalamin cofactor in addition to the [4Fe-4S] cluster that is characteristic of RS enzymes. However, their poor solubility upon overexpression and their generally poor turnover has hampered detailed in vitro studies of these enzymes. It has been suggested that improper folding, possibly caused by insufficient cobalamin during their overproduction in Escherichia coli, leads to formation of inclusion bodies. Herein, we report our efforts to improve the overproduction of class B RS methylases in a soluble form by engineering a strain of E. coli to take in more cobalamin. We cloned five genes (btuC, btuE, btuD, btuF, and btuB) that encode proteins that are responsible for cobalamin uptake and transport in E. coli and co-expressed these genes with those that encode TsrM, Fom3, PhpK, and ThnK, four class B RS methylases that suffer from poor solubility during overproduction. This strategy markedly enhances the uptake of cobalamin into the cytoplasm and improves the solubility of the target enzymes significantly.
Application of DAST mediated reactions in transformations of α-hydroxyphosphonates derived from O-isopropylidene-protected carbohydrate derivatives
Rapp, Magdalena,Mrowiec, Patrycja,Koroniak, Henryk
, p. 745 - 751 (2017)
Various α-hydroxyphosphonates derived from O-isopropylidene glyceraldehyde, hexofuranose and pentofuranose have been prepared to test nucleophilic fluorination reactions. The substrates have been conveniently prepared in Pudovik reactions and the stereose
Bivalent copper complex containing diphosphine ortho-position carborane ligand, preparation method and application thereof
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Paragraph 0029; 0033-0036; 0051-0054, (2020/09/16)
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.
4-furfurylthiopentanone-2 preparation method
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Paragraph 0018; 0078-0081, (2019/11/04)
The invention belongs to the technical field of fine chemistry, and provides a 4-furfurylthiopentanone-2 preparation method, which specifically comprises: adding a raw material chloroacetone to a toluene solution of triphenylphosphine or to triethyl phosphite, and carrying out a heating reflux reaction to obtain a phosphorus salt; dissolving the obtained phosphorus salt in an organic solvent, adding a strong alkali, stirring for 2-3 h, and obtaining phosphorus ylide after completing a reaction; adding the phosphorus ylide to an acetaldehyde aqueous solution or paraldehyde, and stirring until the reaction is completed to obtain 3-pentene-2-ketone; adding piperidine to the 3-pentene-2-ketone, adding a dichloromethane solution of furfuryl mercaptan in a dropwise manner, and controlling the temperature of the system during the adding at 35-40 DEG C; and after the adding, stirring until the reaction is completed so as to obtain the product 4-furfurylthiopentanone-2. According to the present invention, with the method, the problems of high risk, high cost and being unsuitable for industrial production of the 4-furfurylthiopentanone-2 synthesis route in the prior art are solved.
