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Search for "malonate" in Full Text gives 147 result(s) in Beilstein Journal of Organic Chemistry.

Exploring the role of halogen bonding in iodonium ylides: insights into unexpected reactivity and reaction control

  • Carlee A. Montgomery and
  • Graham K. Murphy

Beilstein J. Org. Chem. 2023, 19, 1171–1190, doi:10.3762/bjoc.19.86

Graphical Abstract
  • (Figure 4) [100]. In the dimethyl malonate-derived ylide I-10, the σ-hole opposite the β-dicarbonyl was stronger with an electrostatic potential of 0.084 e, compared to the 0.049 e found for that opposite the arene. The same pattern was observed for the acetylacetone-derived ylide I-11, which possessed
  • leading to malonate, the second equivalent of 31 coupled with the activated amine and cyclized to produce 33. The formation of 35 in their latter study was mechanistically analogous to this proposal; however, a third equivalent of ylide 31 was necessary to facilitate an additional series of PT and SET
  • 44, from which reductive elimination of iodobenzene would generate 40. In 2021, Sen and Gremaud disclosed a blue LED-mediated formal C–H insertion reaction between iodonium ylides (e.g., 31) and pyrroles (e.g., 45), indoles and furans, producing malonate-substituted heterocycles 46 (Scheme 9) [126
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Published 07 Aug 2023

First synthesis of acylated nitrocyclopropanes

  • Kento Iwai,
  • Rikiya Kamidate,
  • Khimiya Wada,
  • Haruyasu Asahara and
  • Nagatoshi Nishiwaki

Beilstein J. Org. Chem. 2023, 19, 892–900, doi:10.3762/bjoc.19.67

Graphical Abstract
  • ) halogenation, and 3) ring closure (Scheme 2). β-Nitrostyrene 2 serves as an appropriate acceptor for conjugate addition by diethyl malonate (3a) to afford adduct 4a, in which the methine group flanked by two carbonyl groups is readily halogenated, and the subsequent intramolecular nucleophilic substitution by
  • nitronic acid furnishes cyclopropane 1a (method a) [1][4][12][13]. Halogenated malonate 6a [7][14][15][16][17] and nitrostyrene 7 [18] can also be used as substrates in this protocol (methods b and c, respectively). In these methods, diesters are mostly used as 1,3-dicarbonyl compounds, with acetylacetone
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Published 21 Jun 2023

Strategies in the synthesis of dibenzo[b,f]heteropines

  • David I. H. Maier,
  • Barend C. B. Bezuidenhoudt and
  • Charlene Marais

Beilstein J. Org. Chem. 2023, 19, 700–718, doi:10.3762/bjoc.19.51

Graphical Abstract
  • 24 was reported by Cong et al. [45] as a method for the synthesis of substituted dibenzo[b,f]oxepines 25 (Scheme 6). Treatment of the malonate derivative 24 with Mn(OAc)3 in 90% acetic acid gave C-10 carboxylate derivatives of dibenzo[b,f]oxepine 25. The authors proposed a one-electron oxidation of
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Published 22 May 2023

Synthesis of medium and large phostams, phostones, and phostines

  • Jiaxi Xu

Beilstein J. Org. Chem. 2023, 19, 687–699, doi:10.3762/bjoc.19.50

Graphical Abstract
  • ]oxazaphosphinin-4-ones (77) and bis(2,2,3,3-tetrafluoropropyl) 2-(4-chlorobenzylidene)malonate (78a) was kept at room temperature for 2 months, giving bis(2,2,3,3-tetrafluoropropyl) 3-(4-chlorophenyl)-2-phenyl/ethoxy-5-oxo-1-phenyl-1,3,5-trihydrobenzo[f][1,2]azaphosphepine-4,4-dicarboxylate 2-oxides (79) in good
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Published 15 May 2023

Photocatalytic sequential C–H functionalization expediting acetoxymalonylation of imidazo heterocycles

  • Deepak Singh,
  • Shyamal Pramanik and
  • Soumitra Maity

Beilstein J. Org. Chem. 2023, 19, 666–673, doi:10.3762/bjoc.19.48

Graphical Abstract
  • each on the pyridine ring. Moreover, IPs with a non-aromatic C-2 substituent like an ester group were also included (4r). We also explored bromo analogues of other active methylenes such as ethyl cyanoacetate, ethyl acetoacetate, dimethyl, and diisopropyl malonates, as extension of diethyl malonate (4s
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Published 12 May 2023

Functionalization of imidazole N-oxide: a recent discovery in organic transformations

  • Koustav Singha,
  • Imran Habib and
  • Mossaraf Hossain

Beilstein J. Org. Chem. 2022, 18, 1575–1588, doi:10.3762/bjoc.18.168

Graphical Abstract
  • arylglyoxals to investigate the scope of substrates. No products were obtained in case of the acyclic CH-acids like dimethyl malonate, acetylacetone, and ethyl acetoacetate under the same conditions. The reaction follows almost the same mechanistic pathway that was previously mentioned as three-component
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Published 22 Nov 2022

Synthesis of 3,4,5-trisubstituted isoxazoles in water via a [3 + 2]-cycloaddition of nitrile oxides and 1,3-diketones, β-ketoesters, or β-ketoamides

  • Md Imran Hossain,
  • Md Imdadul H. Khan,
  • Seong Jong Kim and
  • Hoang V. Le

Beilstein J. Org. Chem. 2022, 18, 446–458, doi:10.3762/bjoc.18.47

Graphical Abstract
  • yields of the reactions with β-ketoesters and β-ketoamides were comparable with those obtained with 1,3-diketones. We also explored the reactions between 4-fluorophenyl hydroximoyl chloride (1a), which was the phenyl hydroximoyl chloride that gave the best yield, and diethyl malonate (2j) or dibenzyl
  • malonate (2k) under the optimized reaction conditions. However, the reactions did not proceed (Figure 5). We suspected that the increased electron-donating effect on both sides of the 1,3-diketones in 2j or 2k made the methylene group less acidic, thus DIPEA was not able to deprotonate the methylene for
  • mmol of 2, and 3 equivalents of DIPEA in 15 mL of 95% water, 5% methanol at room temperature for 2 hours. The yields were calculated after the isolation and purification of products. Reactions between 4-fluorophenyl hydroximoyl chloride (1a) and diethyl malonate (2j) or dibenzyl malonate (2k) did not
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Published 22 Apr 2022

Recent developments and trends in the iron- and cobalt-catalyzed Sonogashira reactions

  • Surendran Amrutha,
  • Sankaran Radhika and
  • Gopinathan Anilkumar

Beilstein J. Org. Chem. 2022, 18, 262–285, doi:10.3762/bjoc.18.31

Graphical Abstract
  • without any remarkable decrease in its catalytic activity. A novel cobalt catalyst with cobalt immobilized on nanochitosan fibers (Co-DMM@MNPs/chitosan) was fabricated using dimethyl malonate [36] and its applicability tested in a Sonogashira coupling reaction. The catalyst was found to be highly active
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Published 03 Mar 2022

Synthesis of novel [1,2,4]triazolo[1,5-b][1,2,4,5]tetrazines and investigation of their fungistatic activity

  • Anna V. Korotina,
  • Svetlana G. Tolshchina,
  • Rashida I. Ishmetova,
  • Natalya P. Evstigneeva,
  • Natalya A. Gerasimova,
  • Natalya V. Zilberberg,
  • Nikolay V. Kungurov,
  • Gennady L. Rusinov,
  • Oleg N. Chupakhin and
  • Valery N. Charushin

Beilstein J. Org. Chem. 2022, 18, 243–250, doi:10.3762/bjoc.18.29

Graphical Abstract
  • modify the triazolo[1,5-b][1,2,4,5]tetrazine ring system with a variety of structural fragments, thus enabling to vary their biological activity. The reactions of new triazolo[1,5-b][1,2,4,5]tetrazines with some CH-active compounds, such as malononitrile, ethyl cyanoacetate and diethyl malonate, have
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Published 01 Mar 2022

Organocatalytic asymmetric nitroso aldol reaction of α-substituted malonamates

  • Ekta Gupta,
  • Narendra Kumar Vaishanv,
  • Sandeep Kumar,
  • Raja Krishnan Purshottam,
  • Ruchir Kant and
  • Kishor Mohanan

Beilstein J. Org. Chem. 2022, 18, 217–224, doi:10.3762/bjoc.18.25

Graphical Abstract
  • hydroxyamination of oxindoles and β-ketoamides [49][50][51][52][53][54]. Recently, it has been shown that malonate derivatives such as malonate half thioesters and malonamides could be effectively used in various enantioselecive addition reactions [55][56][57][58][59][60]. In this context, Chen and co-workers
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Published 21 Feb 2022

Iron-catalyzed domino coupling reactions of π-systems

  • Austin Pounder and
  • William Tam

Beilstein J. Org. Chem. 2021, 17, 2848–2893, doi:10.3762/bjoc.17.196

Graphical Abstract
  • cyclization with the aryl ring constructs the 6-membered heterocyclic framework. In 2015, the Li group investigated the radical addition/cyclization of olefinic malonate and β-diketone compounds 96 with aldehydes 97 (Scheme 19) [97]. The reaction was feasible with ketones; however, lower product yields were
  • observed. The efficiency of the reaction seems to be dependent on the deprotonation of the α-position of the olefinic malonate species. The authors noted decarbonylated products were obtained when cyclohexane carboxaldehyde and pivaldehyde were applied, consistent with the stability of the generated acyl
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Published 07 Dec 2021

Preparation of mono-substituted malonic acid half oxyesters (SMAHOs)

  • Tania Xavier,
  • Sylvie Condon,
  • Christophe Pichon,
  • Erwan Le Gall and
  • Marc Presset

Beilstein J. Org. Chem. 2021, 17, 2085–2094, doi:10.3762/bjoc.17.135

Graphical Abstract
  • describing their preparation. An evaluation of different approaches has been achieved, allowing to define the best strategies to introduce diversity on both the malonic position and the ester function. A classical alkylation step of a malonate by an alkyl halide followed by a monosaponification gave access
  • intermediate Meldrum acid. Both these transformations are characterized by their simplicity and efficiency, allowing a straightforward access to SMAHOs from cheap starting materials. Keywords: alkylation; esterification; malonate; saponification; SMAHO; Introduction Malonic acid half oxyesters (MAHOs), also
  • (SMAHOs) [8][9][10], or disubstituted MAHOs [11], has been only occasionally reported. Bibliographical data indicate that SMAHOs can be accessed by different routes (Scheme 1). The most classic one is the alkylation of a dialkyl malonate, followed by a monohydrolysis of one ester group. The alkylation is
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Published 18 Aug 2021

Asymmetric organocatalyzed synthesis of coumarin derivatives

  • Natália M. Moreira,
  • Lorena S. R. Martelli and
  • Arlene G. Corrêa

Beilstein J. Org. Chem. 2021, 17, 1952–1980, doi:10.3762/bjoc.17.128

Graphical Abstract
  • resulted in products with moderate to excellent yields and enantiomeric excesses as shown in Scheme 16. Enders et al. developed the enantioselective synthesis of cyclopenta[c]-fused chromenones 54 starting from hydroxylated malonate 53 with enals 2 [50]. The reaction stands out for its good to excellent
  • hydroxylated malonate 53 catalyzed by NHC 55. Oxidative [4 + 2] cycloaddition of enals 57 to coumarins 56 catalyzed by NHC 59. Asymmetric [3 + 2] cycloaddition of coumarins 43 to azomethine ylides 60 organocatalyzed by quinidine 62. Synthesis of α-benzylaminocoumarins 64 through Mannich reaction between 4
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Published 03 Aug 2021

Development of N-F fluorinating agents and their fluorinations: Historical perspective

  • Teruo Umemoto,
  • Yuhao Yang and
  • Gerald B. Hammond

Beilstein J. Org. Chem. 2021, 17, 1752–1813, doi:10.3762/bjoc.17.123

Graphical Abstract
  • to form 2-fluoro-2-nitropropane in a 40% yield (Scheme 1). The reaction with sodium diethyl malonate was also reported to produce the difluoromalonate, but in a very low yield of ca. 5%. N-F amine 1-1 is very volatile (bp 49.5 °C), and could only be prepared in 7.5% or 13% yield by electrochemical
  • -fluoropiperidine (1-1) [21] and then in 1991, Banks et al. reported the improved yields of the reactions of 1-1 with sodium salts of 2-nitropropane, malonate esters, and a keto ester, and phenylmagnesium bromide [22]. However, the fluorinated products were still accompanied by considerable amounts of byproducts
  • -rich substrates such as sodium diethyl (phenyl)malonate, 1-morpholinocyclohexene, phenol, and anisole (Scheme 47). The fluorination power of the carboxamide 21-2 was less than that of its N-F sulfonamide analog 11-2. 1-22. N,N’-Difluoro-1,4-diazoniabicyclo[2.2.2]octane salts In 1996, Umemoto and co
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Published 27 Jul 2021

A comprehensive review of flow chemistry techniques tailored to the flavours and fragrances industries

  • Guido Gambacorta,
  • James S. Sharley and
  • Ian R. Baxendale

Beilstein J. Org. Chem. 2021, 17, 1181–1312, doi:10.3762/bjoc.17.90

Graphical Abstract
  • silica are suggested to play a key role in the water elimination step. Furthermore, the primary amine function on the silica shows better outcomes compared to a tertiary amine. Different products were prepared in moderate to excellent yields, however, with the less acidic diethyl malonate the catalyst
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Published 18 May 2021

N-tert-Butanesulfinyl imines in the asymmetric synthesis of nitrogen-containing heterocycles

  • Joseane A. Mendes,
  • Paulo R. R. Costa,
  • Miguel Yus,
  • Francisco Foubelo and
  • Camilla D. Buarque

Beilstein J. Org. Chem. 2021, 17, 1096–1140, doi:10.3762/bjoc.17.86

Graphical Abstract
  • literature, several strategies are reported using the sulfinyl group [84][85][86][87][88]. In this context, an enantioselective synthesis of 4-substituted azetidin-2-ones 52 was also accomplished starting from chiral imines 14 and dimethyl malonate (49). A diastereoselective coupling of these components
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Published 12 May 2021

Application of the Meerwein reaction of 1,4-benzoquinone to a metal-free synthesis of benzofuropyridine analogues

  • Rashmi Singh,
  • Tomas Horsten,
  • Rashmi Prakash,
  • Swapan Dey and
  • Wim Dehaen

Beilstein J. Org. Chem. 2021, 17, 977–982, doi:10.3762/bjoc.17.79

Graphical Abstract
  • presence of a catalytic amount of piperidine afforded pyridopsoralen 22 in 46% yield. Analogously, pyridopsoralen 23 was prepared from 16 by Knoevenagel condensation with diethyl malonate and subsequent lactonization with 62% yield (Scheme 4) [13]. To the best of our understanding, the scaffolds 21–23 are
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Published 30 Apr 2021

Microwave-assisted multicomponent reactions in heterocyclic chemistry and mechanistic aspects

  • Shivani Gulati,
  • Stephy Elza John and
  • Nagula Shankaraiah

Beilstein J. Org. Chem. 2021, 17, 819–865, doi:10.3762/bjoc.17.71

Graphical Abstract
  • first time reported a microwave-assisted four-component domino reaction involving acyclic 1,3-diketones 54, amines 32, diethyl malonate (126) and triethyl orthoformate (111) for the synthesis of substituted pyridone derivatives 127 at 120 °C under catalyst- and solvent-free conditions. The reaction
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Published 19 Apr 2021

[2 + 1] Cycloaddition reactions of fullerene C60 based on diazo compounds

  • Yuliya N. Biglova

Beilstein J. Org. Chem. 2021, 17, 630–670, doi:10.3762/bjoc.17.55

Graphical Abstract
  • CBr4 or I2, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) or NaH as the base, and a malonate-derived substrate. The adduct is synthesized in a slightly higher yield by direct treatment of fullerene with malonates. As noted above, a decrease in the strain of the fullerene core is the driving force of its
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Published 05 Mar 2021

1,2,3-Triazoles as leaving groups: SNAr reactions of 2,6-bistriazolylpurines with O- and C-nucleophiles

  • Dace Cīrule,
  • Irina Novosjolova,
  • Ērika Bizdēna and
  • Māris Turks

Beilstein J. Org. Chem. 2021, 17, 410–419, doi:10.3762/bjoc.17.37

Graphical Abstract
  • transformation into a C–C bond. Compounds containing electron-withdrawing groups such as malonitrile, dimedone, ethyl cyanoacetate and diethyl malonate were used as C-nucleophiles. Transformations were performed in DMF in the presence of NaH and the products were obtained in high yields (Scheme 6). The lower
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Published 11 Feb 2021

The preparation and properties of 1,1-difluorocyclopropane derivatives

  • Kymbat S. Adekenova,
  • Peter B. Wyatt and
  • Sergazy M. Adekenov

Beilstein J. Org. Chem. 2021, 17, 245–272, doi:10.3762/bjoc.17.25

Graphical Abstract
  • -difluorocyclopropanecarboxylic acid derivatives 58 by the Michael addition of ester and amide enolates to 2,4,6-trimethylphenyl 4-bromo-4,4-difluorocrotonate (57) followed by an Et3B-initiated radical cyclization (Scheme 24) [68]. Furthermore, when the sodium salt of dimethyl malonate was used as the Michael donor the
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Published 26 Jan 2021

3-Acetoxy-fatty acid isoprenyl esters from androconia of the ithomiine butterfly Ithomia salapia

  • Florian Mann,
  • Daiane Szczerbowski,
  • Lisa de Silva,
  • Melanie McClure,
  • Marianne Elias and
  • Stefan Schulz

Beilstein J. Org. Chem. 2020, 16, 2776–2787, doi:10.3762/bjoc.16.228

Graphical Abstract
  • leading to the observed regioisomers of the isoprenyl esters. All acids shown were found in form of their isoprenyl esters. (Z)-9-Hexadecenoic acid is obtained from palmitic acid by a Δ9-desaturase (ds). Malonate elongation and reduction (red) leads to (Z)-3-hydroxy-11-octadecenoic acid, an intermediate
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Published 16 Nov 2020

The B & B approach: Ball-milling conjugation of dextran with phenylboronic acid (PBA)-functionalized BODIPY

  • Patrizia Andreozzi,
  • Lorenza Tamberi,
  • Elisamaria Tasca,
  • Gina Elena Giacomazzo,
  • Marta Martinez,
  • Mirko Severi,
  • Marco Marradi,
  • Stefano Cicchi,
  • Sergio Moya,
  • Giacomo Biagiotti and
  • Barbara Richichi

Beilstein J. Org. Chem. 2020, 16, 2272–2281, doi:10.3762/bjoc.16.188

Graphical Abstract
  • third bands in between the spectra in water and in those with the conjugate Dex-1b solution [37]. The I1/I3 of pyrene was 1.1 in water, while in the conjugated dextran solution it was 1.5, a value which is comparable with solvents like diethyl malonate, dioxane, or dimethoxyethane, all organic solvents
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Published 11 Sep 2020

On the hydrolysis of diethyl 2-(perfluorophenyl)malonate

  • Ilya V. Taydakov and
  • Mikhail A. Kiskin

Beilstein J. Org. Chem. 2020, 16, 1863–1868, doi:10.3762/bjoc.16.153

Graphical Abstract
  • General and Inorganic Chemistry, Russian Academy of Sciences, Leninskiy prospect, 31, Moscow, GSP-1, 119991, Russian Federation 10.3762/bjoc.16.153 Abstract Diethyl 2-(perfluorophenyl)malonate was synthesized in 47% isolated yield by the reaction of sodium diethyl malonate and hexafluorobenzene. The
  • surprise, 2-(perfluorophenyl)malonic acid (2) was not described in the literature to date. The only reference to this compound actually concerned the formation of the anion from diethyl 2-(perfluorophenyl)malonate (3) with excess NaH [21]. At the same time, diethyl 2-(perfluorophenyl)malonate (3) is a
  • readily accessible compound. Diethyl 2-phenylmalonate (4) is usually obtained (Scheme 1) by condensation of ethyl phenylacetate (5) and diethyl carbonate under basic conditions [22] because of the low reactivity of bromobenzene in noncatalytic nucleophilic reactions with sodium salts of diethyl malonate
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Published 28 Jul 2020

Pauson–Khand reaction of fluorinated compounds

  • Jorge Escorihuela,
  • Daniel M. Sedgwick,
  • Alberto Llobat,
  • Mercedes Medio-Simón,
  • Pablo Barrio and
  • Santos Fustero

Beilstein J. Org. Chem. 2020, 16, 1662–1682, doi:10.3762/bjoc.16.138

Graphical Abstract
  • , the reaction of dimethyl malonate-derived fluoroaromatic enynes 16 afforded the corresponding cyclopentenone products 17 in higher yields (85–92%). Thus, the reaction of enynes bearing fluorinated groups attached to the alkyne moiety was found to afford the corresponding cyclized products in moderate
  • which they detailed the Markovnikov hydrofluorination of alkynes using HF.DMPU coupled with a gold catalyst [60]. Accordingly, the appropriate propargylmalonate derivatives were fluorinated to give fluoroalkene intermediates, which were then converted into malonate-based enynes 37 (Z = CO2R) through a
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Published 14 Jul 2020
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