Synthesis of 2H-azirine-2,2-dicarboxylic acids and their derivatives

• Anastasiya V. Agafonova,
• Mikhail S. Novikov and
• Alexander F. Khlebnikov

Beilstein J. Org. Chem. 2024, 20, 3191–3197, doi:10.3762/bjoc.20.264

• Anastasiya V. Agafonova Mikhail S. Novikov Alexander F. Khlebnikov Saint Petersburg State University, Institute of Chemistry, 7/9 Universitetskaya Naberezhnaya, St. Petersburg 199034, Russia 10.3762/bjoc.20.264 Abstract Methods for the preparation of 3-aryl-2H-azirine-2,2-dicarboxylic acids and

• chlorides have been developed. Keywords: azirine-2,2-dicarboxamides; azirine-2,2-dicarboxylic acids; isomerization; isoxazoles; Introduction The isomerization of isoxazoles, containing a heteroatomic substituent at C5, to 2H-azirines is a powerful method for the preparation of 2H-azirine-2-carboxylic acid

• only one azirine-2,2-dicarboxylic acid derivative from a certain isoxazole precursor. Herein, we would like to report a method for the synthesis of 2H-azirine-2,2-dicarboxylic acids and their various derivatives from a single starting material, 3-substituted 2H-azirine-2,2-dicarbonyl dichloride 2, via

Tailored charge-neutral self-assembled L₂Zn₂ container for taming oxalate

• David Ocklenburg and
• David Van Craen

Beilstein J. Org. Chem. 2024, 20, 3007–3015, doi:10.3762/bjoc.20.250

• David Ocklenburg David Van Craen Department of Chemistry and Chemical Biology, TU Dortmund University, Otto-Hahn-Straße 6, 44227 Dortmund, Germany 10.3762/bjoc.20.250 Abstract Dicarboxylic acids and their derivatives play crucial roles in various biological processes, necessitating the

• ; metallocontainer; oxalate; Introduction Dicarboxylic acids and their corresponding anions are essential intermediates in the biosynthesis of proteins and important biological metabolites [1][2]. As a result, the development of receptors for this class of compounds is of high interest [3][4][5]. Oxalate, the

Access to cyclopropanes with geminal trifluoromethyl and difluoromethylphosphonate groups

• Ita Hajdin,
• Romana Pajkert,
• Mira Keßler,
• Jianlin Han,
• Haibo Mei and
• Gerd-Volker Röschenthaler

Beilstein J. Org. Chem. 2023, 19, 541–549, doi:10.3762/bjoc.19.39

• obtained by the deoxofluorination of the corresponding dicarboxylic acids with sulfur tetrafluoride, thiophilic ring-opening reactions with nucleophiles or reactions of donor-substituted furans with bis(trifluoromethyl)-substituted ethylenes (Scheme 1D) [41][42][43]. The lack of application of highly

Discrimination of β-cyclodextrin/hazelnut (Corylus avellana L.) oil/flavonoid glycoside and flavonolignan ternary complexes by Fourier-transform infrared spectroscopy coupled with principal component analysis

• Nicoleta G. Hădărugă,
• Gabriela Popescu,
• Dina Gligor (Pane),
• Cristina L. Mitroi,
• Sorin M. Stanciu and
• Daniel Ioan Hădărugă

Beilstein J. Org. Chem. 2023, 19, 380–398, doi:10.3762/bjoc.19.30

• was demonstrated by both thermal (TG–DTG and DSC) and chromatographic (GC–MS for the degradation compounds, i.e., aldehydes, formylated carboxylic acids, or dicarboxylic acids) methods [16]. Also, vegetable oils containing unsaturated FA moieties were stabilized by CD complexation. Common bean

Design, synthesis and application of carbazole macrocycles in anion sensors

• Alo Rüütel,
• Ville Yrjänä,
• Sandip A. Kadam,
• Indrek Saar,
• Mihkel Ilisson,
• Astrid Darnell,
• Kristjan Haav,
• Tõiv Haljasorg,
• Lauri Toom,
• Johan Bobacka and
• Ivo Leito

Beilstein J. Org. Chem. 2020, 16, 1901–1914, doi:10.3762/bjoc.16.157

• using dicarboxylic acids alongside EDC·HCl, HOBT and DMAP/DIPEA. This method was accompanied with a systematic decrease of the yield with the lengthening of the –CH2– methylene bridge. To counteract the decrease of yield a second approach was adapted for the larger receptors MC011–MC014. For this the

• corresponding dicarboxylic acids were first converted to the diacyl chlorides, which were then used for cyclization. This mitigated the yield drop and provided access to the higher macrocycles MC011–MC014. In addition, three other receptor molecules were prepared. MC001 and MC002 were prepared using CDI

Mechanochemical green synthesis of hyper-crosslinked cyclodextrin polymers

• Alberto Rubin Pedrazzo,
• Fabrizio Caldera,
• Marco Zanetti,
• Silvia Lucia Appleton,
• Nilesh Kumar Dhakar and
• Francesco Trotta

Beilstein J. Org. Chem. 2020, 16, 1554–1563, doi:10.3762/bjoc.16.127

• allow them to act as polyfunctional monomers, permitting the crosslinking with bi- or multifunctional chemicals, such as dianhydrides, diisocyanates, diepoxides, and dicarboxylic acids, etc. The polarity and size of the polymer network can be easily tuned by varying the type of the crosslinker and

The use of isoxazoline and isoxazole scaffolding in the design of novel thiourea and amide liquid-crystalline compounds

• Itamar L. Gonçalves,
• Rafaela R. da Rosa,
• Vera L. Eifler-Lima and
• Aloir A. Merlo

Beilstein J. Org. Chem. 2020, 16, 175–184, doi:10.3762/bjoc.16.20

• dissimilar moieties, such as alkyloxybenzoic acids [31] and alkylbenzoic and dodecane dicarboxylic acids [32]. The thioureas, with a perfluorinated chain, 17b and 18b, presented thermal decomposition according to the DSC graphs, at temperatures above 200 °C. These compounds were not analyzed by termal

Synthesis of dipolar molecular rotors as linkers for metal-organic frameworks

• Sebastian Hamer,
• Fynn Röhricht,
• Marius Jakoby,
• Ian A. Howard,
• Xianghui Zhang,
• Christian Näther and
• Rainer Herges

Beilstein J. Org. Chem. 2019, 15, 1331–1338, doi:10.3762/bjoc.15.132

• subsequent direct conversion of the TMS-protected acetylenes to the dicarboxylic acids using a method of Kondo and co-workers [42]. Following this procedure, purification of TMS-protected compounds was more convenient as compared to the tedious work-up with carboxylic acid derivatives directly obtained from

• cross coupling. Using this method, dicarboxylic acids could be obtained from simple aqueous work-up and extraction. Difluoro compound 1 Difluorobenzenes have been employed as dipolar rotors by Garcia-Garibay in crystals [10], as an elongated MOF linker by Blight and Forgan [25] and for the investigation

• , conversion into the respective dicarboxylic acids 4 and 5 took place by reaction with cesium fluoride under a carbon dioxide atmosphere. Conclusion In summary, we reported here the synthesis of five dipolar rotors consisting of a push–pull-substituted phenylene core, with two ethynyl units in para-position

Steroid diversification by multicomponent reactions

• Leslie Reguera,
• Cecilia I. Attorresi,
• Javier A. Ramírez and
• Daniel G. Rivera

Beilstein J. Org. Chem. 2019, 15, 1236–1256, doi:10.3762/bjoc.15.121

• . Thus, cholanic dicarboxylic acids 73 and 74 were macrocyclized with a paraformaldehyde-derived diimine and two different aryl diisocyanides to furnish steroidal cages 75 and 76 in good yields considering the structural complexity created in a single synthetic operation. It is worth mentioning that due

Synthesis of (macro)heterocycles by consecutive/repetitive isocyanide-based multicomponent reactions

• Angélica de Fátima S. Barreto and
• Carlos Kleber Z. Andrade

Beilstein J. Org. Chem. 2019, 15, 906–930, doi:10.3762/bjoc.15.88

• to be used directly to obtain macrocycles of this complexity and size. The synthesis of macrocycles with up to 16 new bonds being formed simultaneously has been described (Scheme 22). The strategy was based on combining steroidal dicarboxylic acids 115 and biaryl ether diisocyanide 116 [38]. The

The LANCA three-component reaction to highly substituted β-ketoenamides – versatile intermediates for the synthesis of functionalized pyridine, pyrimidine, oxazole and quinoxaline derivatives

• Tilman Lechel,
• Roopender Kumar,
• Mrinal K. Bera,
• Reinhold Zimmer and
• Hans-Ulrich Reissig

Beilstein J. Org. Chem. 2019, 15, 655–678, doi:10.3762/bjoc.15.61

• . Enantiopure nitriles or carboxylic acids can also be employed leading to chiral KE with high enantiopurity and dinitriles or dicarboxylic acids also lead to the expected bis-β-ketoenamides. β-Ketoenamides incorporate a unique combination of functional groups and hence a manifold of subsequent reactions to

• of 20% probably due to solubility problems with employed aromatic dinitriles. Nevertheless, these examples showed the feasibility of this approach to highly substituted β-ketoenamides. Similar results were obtained by the use of aromatic dicarboxylic acids (Scheme 6). Again, the moderate efficacy may

• compatible with all kinds of substituents R2 and R3 and several functional groups within these substituents. Enantiopure components efficiently lead to products with stereogenic centers. Dinitriles or dicarboxylic acids provide the expected bis-β-ketoenamides in moderate yield. The prepared β-ketoenamides KE

From dipivaloylketene to tetraoxaadamantanes

• Gert Kollenz and
• Curt Wentrup

Beilstein J. Org. Chem. 2018, 14, 1–10, doi:10.3762/bjoc.14.1

• in isolable enol intermediates of type 9 [18]. The carboxylate cannot form in the presence of an acid and therefore decarboxylation does not take place (17 → 18 → 10). The mono- and dicarboxylic acids 10 and 11 are stable and do not decarboxylate easily. However, aromatic amines carrying strongly

Intramolecular glycosylation

• Xiao G. Jia and
• Alexei V. Demchenko

Beilstein J. Org. Chem. 2017, 13, 2028–2048, doi:10.3762/bjoc.13.201

• seems to have wide applicability…” and disclosed their attempts to link the reaction counterparts with dicarboxylic acids. This served as an ultimate perspective on future developments in the field, but about a decade had passed before Ziegler resurrected this concept. Flexible succinoyl and related

• other flexible linkers investigated are carbonate [57], as well as oxalic [57], malonic [53][57][58], and glutaric [59] dicarboxylic acids. However, like in the case of succinoyl linkers, higher flexibility led to more relaxed stereoselectivity. Further variations upon this method involved the

Rearrangements of organic peroxides and related processes

• Ivan A. Yaremenko,
• Vera A. Vil’,
• Dmitry V. Demchuk and
• Alexander O. Terent’ev

Beilstein J. Org. Chem. 2016, 12, 1647–1748, doi:10.3762/bjoc.12.162

• 25, dicarboxylic acids 28, carboxylic acids 26, and keto carboxylic acids 27 (Scheme 7, Table 1) [223]. The oxidation of isophorone oxide (29) is an industrial process for the production of dimethylglutaric acid 30 (Scheme 8) [223]. Acyl phosphate 32 can be synthesized from acyl phosphonate 31 in

• 105a–g with performic acid generated in situ provides a new route to dicarboxylic acids 106a–g and hydroxycarboxylic acids 107a–g (Table 8) [286]. The proposed mechanism of the oxidation of acetal 105f is shown in Scheme 34. In the first step of the reaction, the elimination of methanol from 105f and

A quadruple cascade protocol for the one-pot synthesis of fully-substituted hexahydroisoindolinones from simple substrates

• Hong-Bo Zhang,
• Yong-Chun Luo,
• Xiu-Qin Hu,
• Yong-Min Liang and
• Peng-Fei Xu

Beilstein J. Org. Chem. 2016, 12, 253–259, doi:10.3762/bjoc.12.27

• isoindolinones have been developed. The first method was the synthesis of 3-substituted isoindolinones from the corresponding N-methylmaleimides by the Diels–Alder reaction with 1,3-butadiene followed by hydrogenation. The second and the third methods employed the corresponding dicarboxylic acids and the

Dicarboxylic esters: Useful tools for the biocatalyzed synthesis of hybrid compounds and polymers

• Ivan Bassanini,
• Karl Hult and
• Sergio Riva

Beilstein J. Org. Chem. 2015, 11, 1583–1595, doi:10.3762/bjoc.11.174

• ; dicarboxylic acids; lipase; polyesters; regioselectivity; Introduction The finding that enzymes can work in organic solvents has significantly expanded the scope of preparative scale biocatalyzed transformations [1][2][3][4]. An uncountable number of reports have been published on this topic since the

• panel of different acylating agents and hydrolases [10][11][12]. Among the great number of investigated acyl donors, activated esters of dicarboxylic acids have been found to be particularly versatile for the production of bifunctionalized compounds. As it will be discussed in the following paragraphs

• parent compound 12. A similar approach was followed later on by Lin and coworkers, who described the enzymatic esterification of the nucleoside 5-fluorouridine (13) and of other polyhydroxylated bioactive molecules with divinyl esters of dicarboxylic acids [31][32][33][34][35]. The monovinyl esters

Preparative semiconductor photoredox catalysis: An emerging theme in organic synthesis

• David W. Manley and
• John C. Walton

Beilstein J. Org. Chem. 2015, 11, 1570–1582, doi:10.3762/bjoc.11.173

• %. Remarkably, incorporation of a second fluorine substituent at the same position in α,α-difluorophenylacetic acid essentially shut down the reaction. SCPC of acids with unprotected R1 = OH or NH2 followed other reaction channels. SCPC of dicarboxylic acids with suitably designed architectures seemed to offer

Electrocarboxylation: towards sustainable and efficient synthesis of valuable carboxylic acids

• Roman Matthessen,
• Jan Fransaer,
• Koen Binnemans and
• Dirk E. De Vos

Beilstein J. Org. Chem. 2014, 10, 2484–2500, doi:10.3762/bjoc.10.260

• -butadiene in a two-compartment cell with a mercury cathode and a platinum anode, giving a mixture of mono- and dicarboxylic acids. CO2 bubbling through a catholyte solution of 1 wt % water in DMF, saturated with butadiene, yielded up to 50% of 3-hexenedioic acid [45], a result which unfortunately was

Homochiral BINOL-based macrocycles with π-electron-rich, electron-withdrawing or extended spacing units as receptors for C₆₀

• Marco Caricato,
• Silvia Díez González,
• Idoia Arandia Ariño and
• Dario Pasini

Beilstein J. Org. Chem. 2014, 10, 1308–1316, doi:10.3762/bjoc.10.132

• several homochiral macrocycles has been achieved by using π-electron-rich, electron-deficient or extended aromatic dicarboxylic acids in combination with an axially-chiral dibenzylic alcohol, derived from enantiomerically-pure BINOL. Two series of cyclic adducts with average molecular D2 and D3 molecular

• ] macrocycles (compounds 3 and 4 in Scheme 1) were obtained. The compounds have average molecular D2 and D3 point group symmetries, respectively. Our optimized esterification reaction protocol is carried out at intermediate dilution levels (each reagent 20–25 mM) in CH2Cl2. Several dicarboxylic acids with

The Flögel-three-component reaction with dicarboxylic acids – an approach to bis(β-alkoxy-β-ketoenamides) for the synthesis of complex pyridine and pyrimidine derivatives

• Mrinal K. Bera,
• Moisés Domínguez,
• Paul Hommes and
• Hans-Ulrich Reissig

Beilstein J. Org. Chem. 2014, 10, 394–404, doi:10.3762/bjoc.10.37

• extension of the substrate scope of the Flögel-three-component reaction of lithiated alkoxyallenes, nitriles and carboxylic acids is presented. The use of dicarboxylic acids allowed the preparation of symmetrical bis(β-ketoenamides) from simple starting materials in moderate yields. Cyclocondensations of

• nitriles is retained during this reaction [40]. In the present report we describe our efforts to further broaden the substrate scope of this multicomponent reaction and the subsequent cyclizations by employing aromatic dicarboxylic acids. This extension should allow a rapid access to fairly complex

• . Hence this experimental result is in perfect agreement with the DFT calculations. Conclusion We were able to extend the substrate scope of the Flögel-three-component reaction of alkoxyallenes, nitriles and carboxylic acids by successfully utilizing aromatic dicarboxylic acids to prepare three new bis(β

Similarity analysis, synthesis, and bioassay of antibacterial cyclic peptidomimetics

• Workalemahu M. Berhanu,
• Mohamed A. Ibrahim,
• Girinath G. Pillai,
• Alexander A. Oliferenko,
• Levan Khelashvili,
• Farukh Jabeen,
• Bushra Mirza,
• Farzana Latif Ansari,
• Ihsan ul-Haq,
• Said A. El-Feky and
• Alan R. Katritzky

Beilstein J. Org. Chem. 2012, 8, 1146–1160, doi:10.3762/bjoc.8.128

• economic synthetic route, renders scaffold 37 as a promising platform for further rational drug design. Synthesis Treatment of dicarboxylic acids 34a–c by a standard method [36] using thionyl chloride and 1H-benzotriazole gave the corresponding benzotriazole derivatives in 37–54% yield (Scheme 1, see

Chiral gels derived from secondary ammonium salts of (1R,3S)-(+)-camphoric acid

• Tapas Kumar Adalder,
• N. N. Adarsh,
• Ravish Sankolli and
• Parthasarathi Dastidar

Beilstein J. Org. Chem. 2010, 6, 848–858, doi:10.3762/bjoc.6.100

• protons of the dicarboxylic acids were absent as was evident from the presence of the characteristic band of COO− (1622–1635 cm−1) and absence of COOH (1699 cm−1) in salts 1, 2, 4 and 5. However, the presence of FT-IR bands at 1701, 1631 cm−1 for salt 3, 1705, 1548 cm−1 for salt 6 and 1701, 1620 cm−1 for

Molecular recognition of organic ammonium ions in solution using synthetic receptors

• Andreas Späth and
• Burkhard König

Beilstein J. Org. Chem. 2010, 6, No. 32, doi:10.3762/bjoc.6.32

Quinoline based receptor in fluorometric discrimination of carboxylic acids

• Kumaresh Ghosh,
• Suman Adhikari,
• Asoke P. Chattopadhyay and
• Purnendu Roy Chowdhury

Beilstein J. Org. Chem. 2008, 4, No. 52, doi:10.3762/bjoc.4.52

• dicarboxylic acids from aliphatic dicarboxylic acids and even long chain aliphatic dicarboxylic acids from short chain aliphatic dicarboxylic acids. The receptor 1 is found to be selective for citric acid with a strong excimer emission in CHCl3. On the contrary, the receptor 2 exhibited less binding constant

• - and dicarboxylic acids by a large number of receptors of different architectures is known [11][12][13][14]. We have also reported a series of synthetic receptors for carboxylic acids of various types [15][16][17][18]. In continuation, we report here a new quinoline based sensor 1 (Figure 1) which is

• more -OH groups in the backbone, exhibits a value of 1.55 × 105 M−1 which is slightly less than tartaric and citric acids. The non-hydroxy dicarboxylic acids such as succinic, glutaric, terephthalic acids bind weakly compared to the hydroxy acids. Besides the dilution method we also followed a

Crystal engineering of analogous and homologous organic compounds: hydrogen bonding patterns in trimethoprim hydrogen phthalate and trimethoprim hydrogen adipate

• Packianathan Thomas Muthiah,
• Savarimuthu Francis,
• Urszula Rychlewska and
• Beata Warżajtis

Beilstein J. Org. Chem. 2006, 2, No. 8, doi:10.1186/1860-5397-2-8

• ] other types of hydrogen-bonded networks are present. The hydrogen-bonding networks in the crystal structures of TMP/pyrimethamine salts of various dicarboxylic acids have been investigated in our laboratory [13][21]. Recently we have also reported a novel isomorphism [21]. The crystal structures of