- Tandem Nenitzescu Reaction/Nucleophilic Aromatic Substitution to Form Novel Pyrido Fused Indole Frameworks
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5-Hydroxyindoles are privileged structures that form part of various bioactive compounds. The Nenitzescu reaction of quinones and enamines is one of the most powerful methods to obtain 5-hydroxyindoles. In this work, we have applied the Nenitzescu reaction to 2-(2-chloropyrid-3-yl)benzoquinones. Mixtures of regioisomers were obtained that could be separated in the 4- and 6-substituted analogues, and then cyclized separately in a metal-free base-catalyzed reaction, affording novel tetracyclic indole derivatives. These are indeed the first examples reported in the literature of the linear pyrido[3′,2′ : 4,5]furo[3,2-b]indole and angular 1H-pyrido[2′,3′ : 4,5]furo[2,3-c]indole systems. The regioselectivity and the yield of the Nenitzescu reaction were found to be dependent on the N-substituent at the enamine. Furthermore, we analyzed the UV-Vis and PL spectra of the new systems, and this was supported by DFT calculations, allowing us to compare the properties of angular compared to linearly shaped compounds.
- Bhatia, Harshita,Debroye, Elke,Dehaen, Wim,Dey, Swapan,Prakash, Prabhat,Singh, Rashmi
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p. 4865 - 4875
(2021/09/22)
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- 6H-benzopyrano[3,4-b]quinoline compounds as well as preparation method and application thereof
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The invention relates to new 6H-benzopyrano[3,4-b]quinoline compounds as well as a preparation method and application thereof in preparation of antitumor drugs. The chemical general formulas of the compounds are shown as structural formulas (I) and (II). In-vitro anti-tumor activity screening results show that the compounds represented by the formula I and the formula II have broad-spectrum anti-tumor activity, and have strong inhibition activity on human colorectal cancer (HCT116), human liver cancer (HepG2), human pancreatic cancer (SW1990), human ovarian cancer (A2780), human breast cancer(MCF7) and human cervical cancer (Hela). Compounds 7h and 7n have relatively strong anti-inhibition activity on a HepG2 cell line, and IC50 of the compounds is 0.58 [mu]M and 1.94 [mu]M respectively and is remarkably superior to that of a control drug irinotecan; a compound 7a has high selectivity on a Hela cell line, and IC50 is 4.37 [mu]M; and compounds 9h and 9i have strong inhibition effects on six tumor cell lines, and the IC50 values are 6.38-21.04 [mu]M and 5.12-23.31 [mu]M respectively. Therefore, the compounds can be used for preparing anti-tumor drugs.
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Paragraph 0018; 0020-0023
(2021/01/29)
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- Facile one-pot multicomponent synthesis of highly functionalized tetrahydropyridines using thiamine hydrochloride as an organocatalyst
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Thiamine hydrochloride (VitB1) has been found to be an efficient catalyst for the multicomponent synthesis of highly functionalized tetrahydropyridines from the reaction of β-ketoester, aromatic aldehydes and anilines. VitB1 is easily available, cheap, and eco benign.
- Singh, Sandeep,Gupta, Annah,Kapoor, Kamal K.
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supporting information
p. 1056 - 1063
(2020/03/04)
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- 5-Hydroxyindole-based EZH2 inhibitors assembled via TCCA-catalyzed condensation and Nenitzescu reactions
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5-Hydroxyindole derivatives have various demonstrated biological activities. Herein, we used 5-hydroxyindole as a synthetic starting point for structural alterations in a combinatorial process to synthesize 22 different compounds with EZH2 inhibitor pharmacophores. A series of 5-hydroxyindole-derived compounds were screened inhibitory activities against K562 cells. According to molecular modeling and in vitro biological activity assays, the preliminary structure-activity relationship was summarized. Compound L–04 improved both the H3K27Me3 reduction and antiproliferation parameters (IC50 = 52.6 μM). These findings revealed that compound L–04 is worthy of consideration as a lead compound to design more potent EZH2 inhibitors. During the preparation of compounds, we discovered that trichloroisocyanuric acid (TCCA) is a novel catalyst which demonstrates condensation-promoting effects. To gain insight into the reaction, in situ React IR technology was used to confirm the reactivity. Different amines were condensed in high yields with β-diketones or β-ketoesters in the presence of TCCA to afford the corresponding products in a short time (10~20 min), which displayed some advantages and provided an alternative condensation strategy.
- Chen, Guoliang,Du, Fangyu,Sun, Wenjiao,Wang, Lihui,Wu, Chunfu,Yang, Cheng,Zhou, Qifan
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- Profiling structural diversity and activity of 2-alkyl-4(1H)-quinoloneN-oxides ofPseudomonasandBurkholderia
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We synthesized all major saturated and unsaturated 2-alkyl-4(1H)-quinoloneN-oxides ofPseudomonasandBurkholderia, quantified their native production levels and characterized their antibiotic activities against competingStaphylococcus aureus. We demonstrate that quinolone core methylation and position of unsaturation in the alkyl-chain dictate antibiotic potency which supports the proposed mechanism of action.
- B?ttcher, Thomas,Dieterich, Cora Lisbeth,Prothiwa, Michaela,Szamosvári, Dávid
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supporting information
p. 6328 - 6331
(2020/06/21)
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- Multicomponent reaction for the synthesis of highly functionalized piperidine scaffolds catalyzed by TMSI
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An efficient method for the synthesis of highly functionalized piperidines via one-pot domino reaction of β-ketoesters, aromatic aldehydes, and aromatic amines was reported. This multicomponent coupling was catalyzed by TMSI in methanol at room temperature, giving desired substituted pyridines in moderate to good yields.
- Wu, Lisha,Yan, Shiqiang,Wang, Wensheng,Li, Yinta
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p. 4311 - 4322
(2020/07/13)
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- Redox Property of Enamines
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Enamines are electron-rich compounds bearing intriguing redox properties. Herein, a series of secondary enamines condensed from primary amine and β-ketocarbonyls were synthesized and their electrochemical oxidation properties were systematically studied by cyclic voltammetry. Furthermore, theoretical calculation of oxidation potentials of enamines, particularly those catalytic intermediates, was also conducted to further broaden the scope investigated. Possible structural factors on oxidation and the nature of the resulted radical cation intermediates were revealed and discussed. Correlation of redox potentials with molecular properties such as highest occupied molecular orbital energies and natural population analysis charge were explored, and there appears no simple linear correlation. On the other hand, a good correlation with Mayr's nucleophilicity parameter N was noted among a range of catalytically relevant enamines. Spin population analysis disclosed that enamine radical cations mainly exhibit the carbon-center free radical feature. Taking experimental and computation data together, a comprehensive picture about the redox property of enamines is presented, which would provide guidance in the development of oxidative enamine catalysis and transformations.
- Li, Yao,Wang, Dehong,Zhang, Long,Luo, Sanzhong
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p. 12071 - 12090
(2019/10/11)
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- Structure-activity relationships and mechanistic studies of novel mitochondria-targeted, leishmanicidal derivatives of the 4-aminostyrylquinoline scaffold
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A new class of quinoline derivatives, bearing amino chains at C-4 and a styryl group at C-2, were tested on Leishmania donovani promastigotes and axenic and intracellular Leishmania pifanoi amastigotes. The introduction of the C-4 substituent improves the activity, which is due to interference with the mitochondrial activity of the parasite and its concomitant bioenergetic collapse by ATP exhaustion. Some compounds show a promising antileishmanial profile, with low micromolar or submicromolar activity on promastigote and amastigote forms and a good selectivity index.
- Staderini, Matteo,Piquero, Marta,Abengózar, María ángeles,Nachér-Vázquez, Montserrat,Romanelli, Giulia,López-Alvarado, Pilar,Rivas, Luis,Bolognesi, Maria Laura,Menéndez, J. Carlos
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supporting information
p. 38 - 53
(2019/03/26)
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- Copper-Catalyzed Site-Selective Oxidative C?C Bond Cleavage of Simple Ketones for the Synthesis of Anilides and Paracetamol
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A copper-catalyzed approach for the N-acylation of anilines with acetone and acetophenones via C?C bond cleavage is described. Under the developed conditions both CHCl3 and CH2Cl2 were identified as potential C1-source to promote the transformation. The reaction features a site selective C?C bond cleavage to install the amide moieties with high functional-group compatibility and wide substrate scope. The developed method avoids the use of sensitive and narcotic agents. The method also represents an excellent complement to the previous protocols with lower E-factor (13.91 mg/1 mg) than current industrially used method (E-factor 17.54 mg/1 mg). The developed approach has also been extended for the effective preparation of pyridine derivatives and paracetamol in gram scale. The course of the reaction was monitored by 1H NMR as a preliminary investigation of the reaction mechanism. (Figure presented.).
- Vodnala, Nagaraju,Gujjarappa, Raghuram,Hazra, Chinmoy K.,Kaldhi, Dhananjaya,Kabi, Arup. K.,Beifuss, Uwe,Malakar, Chandi C.
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p. 135 - 145
(2018/12/05)
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- Citrus juice: Green and natural catalyst for the solvent-free silica supported synthesis of β-enaminones using grindstone technique
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Aim and Objective: Citrus Juice as an efficient, cost-effective and green catalyst employed for one-pot synthesis of various β-substituted enaminones through the reaction of β-dicarbonyl compounds with different primary amines in a solvent-free conditions on silica gel as solid surface using grindstone technique in high yields and short reaction times. The presented procedure is operationally simple, practical and green. Material and Methods: The wide application of this procedure is demonstrated by the use of various substituted amines to react with β-dicarbonyl compounds. The method was successfully applied for primary amines (15 entries) and the related enaminones were well synthesized in good to excellent yields. Melting points were measured on an Electro thermal 9100 apparatus. 1HNMR and 13C NMR spectra were recorded on a FTNMR BRUKER DRX 500 Avence spectrometer. Chemical shifts were given in ppm from TMS as internal references and CDCl3 was used as the solvent as well. The IR spectra were recorded on a Perkin Elmer FT-IR GX instrument. The chemicals used in this work were purchased from Merck and Fluka chemical companies. Results: Grinding synthesis of citrus juice catalyzed enamination of 1,3-dicarbonyls (acetylacetone, methyl and ethyl-3-oxobutanoate) with various primary amines (aromatic and aliphatic) under solvent-free silica supported conditions was examined and studied (15 entries) and the obtained enaminones were well synthesized in good to excellent yields. Furthermore, the effect of various catalysts on the yield and reaction time for grinding synthesis of 3-phenylamino-but-2-enoic acid ethyl ester (1) by this method has evaluated as well. Conclusion: a novel, efficient and green protocol for the grinding synthesis of enaminones using citrus juice as natural catalyst has been presented. This methodology is user friendly, green and low cost procedure under mild reaction condition with faster reaction rates. The citrus juice is inexpensive and non-toxic which makes the process convenient, more economic and benign. Furthermore, applying grindstone technique in solvent-free conditions, use of silica gel as a solid and heterogeneous surface in reaction, high yields of products, cleaner reaction profiles, and availability of the reagents makes this method a better choice for synthetic chemists.
- Marvi, Omid,Fekri, Leila Zare
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- 2,4-Bis(fluoroalkyl)quinoline-3-carboxylates as Tools for the Development of Potential Agrochemical Ingredients
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Based on an easy and scalable method for the synthesis of quinoline derivatives substituted by fluorinated groups at both the C-2 and C-4 positions developed in our laboratory, we have devised an approach to the synthesis of a new series of unprecedented 2,4-bis(fluoroalkyl)quinoline-3-carboxylates in just two steps. After standard saponification, the latter gave the corresponding 2,4-bis(fluoroalkyl)quinoline-3-carboxylic acids, which served as pivotal intermediates for post-functionalization reactions. Indeed, the carboxylic group could then be derivatized according to known procedures to introduce chemical diversity at the C-3 position of these unprecedented structures. The resulting highly functionalized quinolines can serve as a platform for the development of biologically active molecules with strong potential for agrochemical research.
- Aribi, Fallia,Panossian, Armen,Vors, Jean-Pierre,Pazenok, Sergii,Leroux, Frédéric R.
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p. 3792 - 3802
(2018/05/16)
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- PROCESS FOR THE PREPARATION OF 2,3,4-TRISUBSTITUTED QUINOLINES
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The invention relates to a process for preparing 2,3,4-trisubstituted quinolines from ketimines and haloalkylamino reagents.
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Page/Page column 9
(2019/01/15)
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- Regiospecific Hydroamination of Unsymmetrical Electron-Rich and Electron-Poor Alkynes with Anilines Catalyzed by Gold(I) Immobilized in MCM-41
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The first heterogeneous gold(I)-catalyzed regiospecific hydroamination of ynamides and propiolic acid derivatives with anilines has been achieved by using a diphenylphosphine-functionalized MCM-41-supported gold (I) complex and AgNTf2 as catalysts under mild conditions, yielding the corresponding (E)-N-arylimines and (Z)-enamines in good to excellent yields with broad substrate scope. The new heterogeneous gold(I) complex can easily be prepared via a two-step procedure from commercially available reagents and recovered by simple filtration of the reaction mixture. The recovered catalyst (Ph2P-MCM-41-AuNTf2) can be reused at least seven times without addition of AgNTf2 as a co-catalyst and its catalytic efficiency remains unaltered. (Figure presented.).
- Liu, Dayi,Nie, Quan,Zhang, Rongli,Cai, Mingzhong
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supporting information
p. 3940 - 3948
(2018/09/14)
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- PIDA/TBAB-Promoted Oxidative Geminal Dibromofunctionalization of Alkynes: Direct Synthesis of Geminal Diazides
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PIDA/TBAB-promoted oxidative geminal diazidofunctionalization of alkynes has been described for the first time. The transformation demonstrates a mechanistically distinctive approach to access geminal diazides, in which TBAB plays a crucial role as brominating agent and for the in situ generation of tetrabutylammonium azide. Furthermore, we have demonstrated here the first cycloaminative strategy by tactically employing the two azides groups leading to quinoxalines and synthesis of bis-triazole derivatives via copper catalysis.
- Arepally, Sagar,Babu, Venkata Nagarjuna,Polu, Ashok,Sharada, Duddu S.
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supporting information
p. 5700 - 5705
(2018/10/15)
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- Assembling Porphyrins into Extended Network Structures by Employing Aromatic Dicarboxylates: Synthesis, Metal Exchange, and Heterogeneous Catalytic Studies
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Three new metal–organic porphyrinic framework compounds of zinc and 5,10,15,20-tetrakis(4-pyridyl)porphyrin (TPyP) have been synthesized under solvothermal conditions. The compounds [Zn5(C40H24N8)(C8H4O4)2(NO3)6(DMA)2] (DMA)3(H2O)8 (1; DMA=dimethylacetamide), [Zn3(C40H24N8)(C8H4O4)2(DMF)](DMF)5(H2O)12 (2), and [Zn3(C40H24N8)(C12H6O4)2(DMA)2](H2O)7 (3) have two (1) and three dimensionally (2 and 3) extended structures. All the three structures contain porphyrinic units connected through the carboxylate linkers. The nitrates bind the metal centers and are not hydrogen bonded. The different binding modes of nitrate in the structure of 1 are observed for the first time in a porphyrin-based MOF. The openness of the structure allowed us to explore metal exchange through a room-temperature metathetic route. Compound 2 undergoes 100 % exchange with copper, whereas compound 3 exchanges 70 % with copper. The copper-exchanged compounds Cu∈2 and Cu∈3 were observed to be good heterogeneous catalysts for many important organic reactions. The chemo and regioselective enamination of β-ketoesters, preparation of propargylamine derivatives as well as regioselective cycloadditions of alkyne and azide (click reactions) have been carried out with good yields and selectivity. All the compounds have been characterized by PXRD, IR, UV/Vis, atomic absorption spectroscopy (AAS), and energy-dispersive X-ray spectroscopy (for Cu exchange).
- Dutta, Gargi,Jana, Ajay Kumar,Natarajan, Srinivasan
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supporting information
p. 8932 - 8940
(2017/07/11)
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- Synthesis of Indoles and Pyrroles Utilizing Iridium Carbenes Generated from Sulfoxonium Ylides
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Metal carbenes can undergo a myriad of synthetic transformations. Sulfur ylides are potential safe precursors of metal carbenes. Herein, we report cascade reactions that involve carbenoids derived from sulfoxonium ylides for the efficient and regioselective synthesis of indoles and pyrroles. The tandem action of iridium and Br?nsted acid catalysts enables rapid assembly of the heterocycles from unmodified anilines or readily accessible enamines under microwave irradiation. The key mechanistic steps are the catalytic transformation of the sulfoxonium ylide into an iridium–carbene complex, followed by N?H or C?H functionalization of an aniline or enamine, respectively, and a final acid-catalyzed cyclization. The present method was successfully applied to the synthesis of the densely functionalized pyrrole subunit of atorvastatin.
- Vaitla, Janakiram,Bayer, Annette,Hopmann, Kathrin H.
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supporting information
p. 4277 - 4281
(2017/04/03)
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- Graphene oxide: A carbocatalyst for the one-pot multicomponent synthesis of highly functionalized tetrahydropyridines
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A simple, straightforward and efficient methodology is described for the synthesis of polysubstituted tetrahydropyridine via one-pot multicomponent reaction of β-ketoester, aldehyde and aniline in presence of catalytic amount of graphene oxide in acetonitrile. Graphene oxide is a versatile carbocatalyst and this is the first report on its application in a five component reaction. Good yield, usage of readily available starting material, operational simplicity, easy work-up and eco-friendly re-usable catalyst are the key features of this protocol.
- Gupta, Annah,Kaur, Ramneet,Singh, Deepika,Kapoor, Kamal K.
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p. 2583 - 2587
(2017/06/13)
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- AlCl3-promoted cyclization of β-keto derivatives with in situ generated enamines under solvent-free high speed ball milling: An efficient one-pot access to polysubstituted 1,4-dihydropyridines
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Under high speed ball milling (HSBM), a simple method for efficient synthesis of structurally diverse polysubstituted 1,4-dihydropyridines is developed via AlCl3-promoted Robinson-like cyclization of β-keto derivatives with in situ generated enamines. This one-pot protocol exhibits the advantages of high chemoselectivity, short reaction time, good functional group tolerance, mild reaction condition and easy work-up.
- Zeng, Ji-Chao,Yu, Fei,Asiri, Abdullah M.,Marwani, Hadi M.,Zhanga, Ze
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p. 2054 - 2064
(2017/11/21)
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- MgFe2O4/cellulose/SO3H nanocomposite: a new biopolymer-based nanocatalyst for one-pot multicomponent syntheses of polysubstituted tetrahydropyridines and dihydropyrimidinones
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A new biopolymer cellulose-based magnetic heterogeneous catalyst, MgFe2O4/cellulose/SO3H nanocomposite, was prepared. Fourier-transform infrared spectra, X-ray diffraction, energy-dispersive X-ray, field-emission scanning electron microscopy, thermal analysis (TG, DTG and DSC), dynamic light scattering and vibrating sample magnetometer measurements have been used to characterize the catalyst. Then, it was applied efficiently as an inexpensive and green catalyst in two multicomponent syntheses of polysubstituted tetrahydropyridines and dihydropyrimidinones under solvent-free conditions. The nanocatalyst can be recovered and reused several times without significant loss of catalytic activity.
- Maleki, Ali,Jafari, Abbas Ali,Yousefi, Somayeh
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p. 1801 - 1813
(2017/06/27)
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- Transformation of One-Dimensional Achiral Structure to Three-Dimensional Chiral Structure: Mechanistic Study and Catalytic Activities of Chiral Structure
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We have isolated two copper-based coordination polymers through solvent diffusion and solvothermal methods using copper salt, furan dicarboxylic acid (FDC), 4,4′-bipyridine (bpy) in MeOH/ethylene glycol, and water solvents. Compound 1 is adopting P21/c space group and adopts a one-dimensional wirelike structure with a free carboxylate anion. Compound 2 crystallizes in chiral space group P65. This is a three-dimensional structure with helical chains. This helicity might be the reason for chiral generation and symmetry breaking. We have converted compound 1 to compound 2 using grinding, followed by a solvothermal method. The circular dichroism data of 2 showed that it is an enantioenriched compound. We have shown that compound 2 is a very good catalyst for chemo- and regioselective enamination reaction and for azide-alkyne Huisgen cycloaddition, respectively.
- Rao, Purna Chandra,Chaudhary, Sonu Pratap,Kuznetsov, Denis,Mandal, Sukhendu
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supporting information
p. 12669 - 12674
(2016/12/26)
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- Synthesis of Quinoxaline Derivatives via Tandem Oxidative Azidation/Cyclization Reaction of N -Arylenamines
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A new method was developed for the synthesis of quinoxalines. This method employs N-arylenamines and TMSN3 as the starting materials and implements two oxidative C-N bond-forming processes in a tandem pattern by using (diacetoxyiodo)benzene as the common oxidant. The present reaction conditions are mild and simple and thus are useful in practical synthesis. (Chemical Equation Presented).
- Ma, Haichao,Li, Dianjun,Yu, Wei
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supporting information
p. 868 - 871
(2016/03/04)
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- Bimetallic Ag-Cu alloy nanoparticles as a highly active catalyst for the enamination of 1,3-dicarbonyl compounds
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Bimetallic nanoparticles, particularly those based on copper, have recently attracted a great deal of attention for the development of low cost and highly active catalysts due to the synergistic interaction between individual metal components. In this work, bimetallic Ag-Cu alloy nanoparticles were explored as a highly active and reusable catalyst for the enamination of 1,3-dicarbonyls using diverse amines. The nanocatalysts were intensively characterized by ultraviolet-visible (UV-Vis) spectroscopy, X-ray diffraction (XRD), high-resolution transmission electron microscopy-energy-dispersive spectroscopy (HRTEM-EDS) and valence band and core level X-ray photoelectron spectroscopy (XPS) to study the effect of the bimetallic structure and composition. In comparison to monometallic Ag and Cu nanoparticles, the alloyed Ag-Cu nanoparticles showed a high catalytic performance and the resultant catalytic activity was dependant on the Ag to Cu ratio. This enhanced catalytic activity should be related to the electronic interaction between Ag and Cu nanoparticles formed due to the intimate contact between them. Our study may serve as a foundation for designing efficient alloyed nanocatalysts for fine chemical synthesis via enamination reactions.
- Rout, Lipeeka,Kumar, Aniket,Dhaka, Rajendra S.,Dash, Priyabrat
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p. 49923 - 49940
(2016/06/15)
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- 'On-Water' Multicomponent Reaction for the Diastereoselective Synthesis of Functionalized Tetrahydropyridines and Mechanistic Insight
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An ecofriendly approach for the synthesis of highly substituted tetrahydropyridines by an 'on-water' multicomponent reaction has been demonstrated. The use of water as the reaction medium is essential under the catalytic influence of a surfactant. The use of a variety of anionic, cationic, and non-ionic surfactants in water was examined and the reaction was successfully catalyzed by anionic surfactants sodium dioctyl sulfosuccinate (SDOSS) and sodium dodecyl sulfate (SDS), with the former being superior. The use of an organic solvent together with a catalytic amount of sodium dioctyl sulfosuccinate to form homogeneous conditions afforded inferior yields and highlighted the specific role of water through the creation of microreactors at the water surfactant interface. A mechanistic insight for the five-component reaction leading to the formation of tetrahydropyridines is provided invoking a tandem inter- and intramolecular Mannich reaction pathway.
- Parikh, Naisargee,Roy, Sudipta Raha,Seth, Kapileswar,Kumar, Asim,Chakraborti, Asit K.
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p. 547 - 556
(2016/02/18)
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- Effect of solvent ratio and counter ions on the morphology of copper nanoparticles and their catalytic application in β-enaminone synthesis
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This work reports the synthesis of shape selective copper nanoparticles (NPs) using a microwave irradiation method, using diverse ratios of an ethylene glycol (EG)/water system. The solvent ratio of EG/water plays a pivotal role in the selective formation of CuO NPs. The alteration of the counter ion of the copper precursor leading to the selective synthesis of copper (CuO, Cu2O, Cu(OH)2) NPs has been observed. The synthesized copper NPs are well characterized using FEG-SEM, TEM, XRD, XPS, NH3-TPD and BET surface area. The prepared CuO NPs show high activity towards the synthesis of β-enaminones and β-enamino esters from 1,3 diketones and amines.
- Gajengi, Aravind L.,Sasaki, Takehiko,Bhanage, Bhalchandra M.
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p. 101800 - 101807
(2016/11/09)
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- Palladium(II)-Catalyzed ortho-Arylation of Aromatic Alcohols with a Readily Attachable and Cleavable Molecular Scaffold
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A palladium(II)-catalyzed C?H arylation process of alcohols has been developed. The strategy utilizes a novel quinoline-based hemiacetal scaffold that can direct the selective C?H bond functionalization. This reaction provides a useful method to construct biaryl compounds of benzyl alcohols in good to excellent yields. The new molecular scaffold can be readily attached, removed, and recovered.
- Li, Qiankun,Knight, Brian J.,Ferreira, Eric M.
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supporting information
p. 13054 - 13058
(2016/09/09)
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- Calix[n]arenes: Active organocatalysts for the synthesis of densely functionalized piperidines by one-pot multicomponent procedure
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An efficient, suitable and high yielding method has been developed for the synthesis of different densely functionalized piperidine derivatives via pseudo-five component, one-pot domino reaction through a combination of β-ketoesters, aromatic aldehydes, and various amines using p-sulfonic acid calix[n]arenes as catalysts. The reaction was carried out in refluxing methanol, affording very good yields of the expected piperidine. Atomic economy, environmentally benign procedure, reuse of catalysts, and short reaction time are some of the important features of this protocol.
- Palermo,Sathicq,Liberto,Fernandes,Langer,Jios,Romanelli
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supporting information
p. 2049 - 2054
(2016/04/26)
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- Hypervalent iodine(III)-promoted: N -incorporation into N -aryl vinylogous carbamates to quinoxaline diesters: Access to 1,4,5,8-tetraazaphenanthrene
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A novel oxidative N-incorporation strategy for synthesis of quinoxaline diesters under metal-free conditions is described for the first time. The mild reaction conditions allow for this transformation via the formation of two C(sp2)-N bonds utilizing cheaply available NaN3 as the N-atom source. N-Aryl vinylogous carbamates in this study undergo azidation at enamino C(sp2)-H selectively. The robustness of this strategy is further demonstrated by the synthesis of a valuable 1,4,5,8-tetraazaphenanthrene derivative using a mild and convenient approach.
- Sagar,Vidaycharan, Shinde,Shinde, Anand H.,Sharada, Duddu S.
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supporting information
p. 4018 - 4022
(2016/06/14)
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- Three naphthalenedisulfonate polymers with imidazole-containing ligands: Synthesis, structure and heterogeneously catalytic performance in reactions of enamination of β-dicarbonyl compounds
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Three new naphthalenedisulfonate polymers, [Cd(2,6-nds)(bib)]n (1), [Cd(1,5-nds)(bib)]n (2), and [Cu(2,6-nds)0.5(tpim)]n (3), have been successfully synthesized by hydrothermal reactions of corresponding metal salts with naphthalenedisulfonate (nds) and imidazole-containing ligands 1,4-bis(imidazol-1-ylmethyl)benzene (bib) and 2,4,5-tri(4-pyridyl)-imidazole (tpim). The structures of these polymers were determined by single crystal X-ray diffraction analysis. Polymers 1 and 2 crystallize in the same space group and have similar cell parameters, and thus show same three-dimensional (3D) framework architecture. Complex 3 has the same 2D layer structure. The photoluminescent properties of the complexes 1 and 2 were investigated. Catalytic tests indicate that complex 3 has chemo-and regio-selective catalytic activity towards enamination of β-ketoesters.
- Wang, Li,Liu, Jing,Guo, Hui,Deng, Dongsheng,Yao, Tian,Wang, Xingwei,Wang, Xinyi,Wu, Hongli
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supporting information
p. 253 - 260
(2015/04/14)
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- Synthesis, spectral and structural characterization of cobalt(III) dithiocarbamato complexes: Catalytic application for the solvent free enamination reaction
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The syntheses, spectral, structural and catalytic properties of some new cobalt(III) complexes, [Co(mpcdt)3] (1), [Co(ppcdt)3] (2) and [Co(mppcdt)3]·0.25CHCl3 (3), derived from 4-methyl piperazine-1-carbodithioate (mpcdt), 4-phenyl piperazine-1-carbodithioate (ppcdt) and 4-(2-methoxyphenyl) piperazine-1-carbodithioate (mppcdt) have been described. A series of β-enaminoesters and β-enaminones were obtained in about 90% yield by the reactions of β-ketoesters and 1,3-diketones with aliphatic and aromatic amines using 1-2 mol% of the above cobalt(III) complexes as catalysts and these have been characterized by NMR, GC-MS and X-ray crystallography. Complexes 1, 2 and 3 are stabilized by intermolecular C-H?S interactions, leading to the formation of supramolecular architectures. Thermogravimetric analysis of complexes 1 and 2 have been investigated by TG-DTA, which indicate that cobalt sulfide is formed as the final product.
- Bharati, Pooja,Bharti,Nath,Bharty,Butcher,Singh
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p. 375 - 385
(2015/11/03)
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- Design of a graphene oxide-SnO2 nanocomposite with superior catalytic efficiency for the synthesis of β-enaminones and β-enaminoesters
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A graphene oxide (GO)-SnO2-based nanocomposite was synthesized by decorating the graphene oxide surface with SnO2 nanoparticles via a solvothermal process. The nanocomposite was characterized using Fourier transform infrared spectra (FTIR), FT-Raman spectroscopy, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Field-emission Scanning electron microscopy (FE-SEM), Energy dispersive X-ray spectroscopy (EDS), Transmission electron microscopy (TEM) and N2 adsorption/desorption study. The FE-SEM and TEM images demonstrate the uniform distribution of the SnO2 nanoparticles on the GO surface and high-resolution transmission electron microscopy (HRTEM) confirms an average particle size of 8-12 nm. The GO-SnO2 nanocomposite has been found to be an extremely efficient catalyst for the synthesis of β-enaminones and β-enaminoesters in methanol solvent and also, in solventless conditions. The GO-SnO2 nanocomposites exhibited synergistically more superior catalytic efficiency compared to pure graphene oxide and SnO2 nanoparticles. The reaction conditions were optimized by changing different parameters such as catalyst, solvent, catalyst loading, and temperature. It has been found that the catalyst gave higher activity under solventless conditions than methanol. The GO-SnO2 composite was recycled for up to four cycles with minimal loss in activity.
- Kumar, Aniket,Rout, Lipeeka,Dhaka, Rajendra S.,Samal, Saroj L.,Dash, Priyabrat
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p. 39193 - 39204
(2015/05/20)
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- Iodine-Promoted Construction of Polysubstituted 2,3-Dihydropyrroles from Chalcones and β-Enamine Ketones (Esters)
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A novel approach for the synthesis of a variety of polysubstituted trans-2,3-dihydropyrroles from a wide range of chalcones and β-enamine ketones (esters) via iodine-promoted tandem Michael/cyclization sequence has been developed, affording the desired products in moderate to excellent yields. This methodology is a highly efficient, convenient way to access functionalized 2,3-dihydropyrroles from readily accessible substrates under mild reaction conditions.
- Li, Yujin,Xu, Hui,Xing, Mengming,Huang, Fang,Jia, Jianhong,Gao, Jianrong
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supporting information
p. 3690 - 3693
(2015/08/18)
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- Fabrication of Ag/γ-Fe2O3@TiO2 hollow magnetic core-shell nanospheres as highly efficient catalysts for the synthesis of β-enaminones
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Herein, we describe a method to prepare hollow magnetic mesoporous sphere catalysts (Ag/γ-Fe2O3@meso-TiO2). The core-shell strategy efficiently prevents the aggregation of Ag NPs in the high temperature calcination process and the leaching of Ag NPs for the catalytic reaction in the liquid phase. The catalyst is characterized by TEM, XRD and ICP-AES. Moreover, the catalyst exhibited improved activity for the synthesis of β-enaminones, and it could be easily recovered by an external magnet from the reaction mixture and recycled five times without any significant loss in activity.
- Huo, Hongfei,Li, Xinzhe,Zhou, Xingchun,Jiao, Lixin,Zhao, Shiling,Zhang, Le,Li, Wenzhu,Li, Shuwen,Li, Rong
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p. 73612 - 73618
(2015/09/15)
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- Highly functionalized tetrahydropyridines are cytotoxic and selective inhibitors of human puromycin sensitive aminopeptidase
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Efficient one-pot five-component synthetic protocols for highly functionalized tetrahydropyridines (THPs) and their biological evaluation have been illustrated. Synthesis of novel functionalized tetrahydropyridines containing differential substitutions at 2,6-positions has been achieved via a modified MCR. Cytotoxic studies of 23 synthesized compounds have been carried out against three different cell lines, namely A-549, HeLa and HepG2, wherein some compounds have displayed appreciable cytotoxicity. Further, investigation of enzyme inhibition by the synthesized THPs has been carried out against four members of M1 family aminopeptidases. Several compounds have selectively inhibited only one member of this enzyme family i.e., human puromycin sensitive aminopeptidase (hPSA). Among the compounds; 4b, 9b, 9e and 10a demonstrated best inhibition against hPSA.
- Aeluri, Raghunath,Ganji, Roopa Jones,Marapaka, Anil Kumar,Pillalamarri, Vijaykumar,Alla, Manjula,Addlagatta, Anthony
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- Base-catalyzed synthesis of amides and imines via C-C and CC bond cleavage
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A transition metal free base catalyzed approach for C-N bond formation via C-C and CC bond activation has been developed. The N-arylureas reacted smoothly with 1,3-dicarbonyls and α,β-unsaturated ketones to furnish the corresponding amides and imines respectively in moderate to excellent yields.
- Yadav, Dilip Kumar T.,Bhanage, Bhalchandra M.
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p. 12387 - 12391
(2015/02/19)
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- Solvent-free synthesis of β-enamino ketones and esters catalysed by recyclable iron(III) triflate
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A novel application of highly stable Fe(OTf)3 as an efficient catalyst for the synthesis of a variety of β-enamino ketones and esters under solvent-free conditions is described. Notably, this protocol of a "green synthesis", which produced β-enamino ketones and esters by the reaction of a variety of β-dicarbonyl compounds and primary amines, exhibits attractive properties including high yields, short reaction periods, lower loading of catalyst and chemo- and regio-selectivity. In addition, the catalyst was easily recovered from the reaction system and readily reused with minimal loss of activity.
- Feng, Cheng-Liang,Chu, Ning-Ning,Zhang, Shu-Guang,Cai, Jin,Chen, Jun-Qing,Hu, Hua-You,Ji, Min
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p. 1097 - 1103
(2014/05/20)
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- Zn[aminoacid]2 hybrid materials applied as heterogeneous catalysts in the synthesis of β-enaminones
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Hybrid materials have seized attention from scientific community mainly as heterogenic catalysts in organic reactions on a large scale succeeding in some organic compounds with high yields. One of the most important classes of hybrid materials used for this purpose involves the complexation of Zn and aminoacids. Herein, we introduced Zn[Pro]2 and Zn[Gly]2 in the synthesis of several β-enaminones via solvent free protocol and using an ultrasound device.
- Winck, Cristiane R.,Darbem, Mariana P.,Gomes, Roberto S.,Rinaldi, Andrelson W.,Domingues, Nelson Luís C.
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supporting information
p. 4123 - 4125
(2014/07/22)
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- Zn[aminoacid]2 hybrid materials applied as heterogeneous catalysts in the synthesis of β-enaminones
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Hybrid materials have seized attention from scientific community mainly as heterogenic catalysts in organic reactions on a large scale succeeding in some organic compounds with high yields. One of the most important classes of hybrid materials used for this purpose involves the complexation of Zn and aminoacids. Herein, we introduced Zn[Pro]2 and Zn[Gly]2 in the synthesis of several β-enaminones via solvent free protocol and using an ultrasound device.
- Winck, Cristiane R.,Darbem, Mariana P.,Gomes, Roberto S.,Rinaldi, Andrelson W.,Domingues, Nelson Luís C.
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supporting information
p. 4123 - 4125
(2015/02/02)
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- A chemoselective route to β-enamino esters and thioesters
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Conditions were developed for syntheses of β-enamino esters, thioesters, and amides. These reactions involve hydroxybenzotriazole derivatives in buffered media. Illustrative syntheses of some heterocyclic systems are given, including some related to protein-protein interface mimics.
- Xin, Dongyue,Burgess, Kevin
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supporting information
p. 2108 - 2110
(2014/05/06)
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- K-10 clay as a reusable catalyst for the solvent-free, MW-induced synthesis of enaminones
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A series of β-amino-a,β-unsaturated ketones and esters were synthesized in good to excellent yields from the reaction of different amines with 1,3-dicarbonyl compounds in solvent-free media using montmorillonite K-10 clay as.
- Marvi, Omid,Giahi, Masoud,Ayub, Pouran Pur,Nikpasand, Mohammad
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p. 921 - 926
(2014/11/07)
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- A general and efficient method for synthesis of enaminones and enamino esters catalyzed by NbCl5 under solvent-free conditions
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A general and simple procedure was developed for the synthesis of β-enaminones and β-enamino esters by reacting 1,3-dicarbonyl compounds with amines in the presence of catalytic amounts of niobium pentachloride. The reaction proceeds smoothly at room temperature under solvent-free conditions and leads to chemo- and regioselective formation of enamine derivatives in high to excellent yields.
- Liu, Yu-Heng,Wang, Ping,Cheng, Gui-Tian
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p. 191 - 196
(2013/07/27)
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- Zinc triflate catalysed synthesis of β-enamino ketones(esters) under solvent-free conditions
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An efficient and mild procedure is described for the synthesis of a series of β-enamino ketones(esters) from 1,3-dicarbonyl compounds and aliphatic and aromatic amines using zinc triflate as the catalyst.
- Feng, Chengliang,Zhang, Shuguang,Cai, Jin,Chen, Junqing,Hu, Huayou,Ji, Min
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p. 626 - 629
(2013/11/06)
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- P2W18O62·24H2O as an efficient and recyclable catalyst for the ecofriendly preparation of β-aminocrotonates
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H6P2W18O62·24H 2O bulk-and silica-supported catalysts were found to be efficient and recyclable catalysts for the synthesis of a series of β-aminocrotonates using toluene as the solvent or under no solvent reaction conditions. Several substituted β-aminocrotonates can be prepared in very good yields and purity by direct reaction of amines and 1,3-dicarbonyl compounds in the presence of a catalytic amount of bulk-and silica-gel-supported H6P 2W18O62·24H2O. The title compounds were prepared in very good yields using both methodologies, and no secondary products were detected. The procedure using no reaction solvent resulted in a clean and useful alternative, which has the advantages of a greener methodology with operative simplicity, the use of a reusable and noncorrosive solid catalyst, soft reaction conditions, low reaction times, and good yields.
- Sanchez, Laura M.,Sathicq, Angel G.,Baronetti, Graciela T.,Thomas, Horacio J.,Romanelli, Gustavo P.
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p. 137 - 142
(2013/06/05)
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- A new copper-based metal-organic framework as a promising heterogeneous catalyst for chemo- and regio-selective enamination of β-ketoesters
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Assembly of 5-nitro-1,2,3-benzenetricarboxylic acid (H3nbta) with CuII in the presence of 1,3-bis(1,2,4-triazol-1-yl)propane (1,3-btp) leads to a new metal-organic framework, [Cu(Hnbta)(1,3-btp)] ·2H2O (A1), which is shown to be an efficient and recyclable heterogeneous catalyst for enamination of β-ketoesters with excellent product yields and selectivity.
- Zhao, Ying,Deng, Dong-Sheng,Ma, Lu-Fang,Ji, Bao-Ming,Wang, Li-Ya
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supporting information
p. 10299 - 10301
(2013/10/22)
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- Ecofriendly and facile Nano ZnO catalyzed solvent-free enamination of 1,3-dicarbonyls
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Nano zinc oxide (Nano-ZnO) was explored as a reusable catalyst for the enamination of 1,3-dicarbonyls using diverse amines. To make the process environmentally viable, the reaction was carried out under solvent-free conditions and found to give good yield of desired products. The catalyst was characterized by various analytical techniques such as UV-spectroscopy, XRD, and TEM. The catalyst was found to be reusable up to four catalytic cycles without any appreciable loss in activity.
- Indulkar, Utkarsha U.,Kale, Sandip R.,Gawande, Manoj B.,Jayaram, Radha V.
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supporting information; experimental part
p. 3857 - 3860
(2012/08/27)
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- Cross-dehydrogenative coupling between enamino esters and ketones: Synthesis of tetrasubstituted pyrroles
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Tetrasubstituted pyrroles have been synthesized via the cross-dehydrogenative coupling between enamino esters and acetone. Silver carbonate proved to be an effective oxidant, and no transition metal catalyst is necessary.
- Zhao, Miao,Wang, Fen,Li, Xingwei
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supporting information; experimental part
p. 1412 - 1415
(2012/05/04)
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- N1-{4-[(10S)-Dihydroartemisinin-10-oxyl]}phenylmethylene-N 2-(2-methylquinoline-4-yl)hydrazine derivatives as antiplasmodial falcipain-2 inhibitors
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A series of N1-{4-[(10S)-dihydroartemisinin- 10-oxyl]}phenylmethylene-N2-(2-methylquinoline-4-yl) hydrazine derivatives 9a-9n possessing 4-quinolylhydrazone and artemisinin cores were herein synthesized and evaluated for their activities against cysteine protease falcipain- 2 of Plasmodium falciparum. The structures were clearly confirmed by elemental analysis, 1H NMR, and mass spectra. The pharmacological results indicated that all compounds showed excellent activity against recombinant falcipain-2 (IC50 = 0.15-2.28 μM). The best one of this series was compound 9d (IC50 = 0.15 μM). The molecular docking results showed that the compound 9d made close contact with the key active site of cysteine protease falcipain-2.
- Luo, Wei,Liu, Yang,Wang, Jian,Guo, Chun,Lu, Wei-Qiang,Cui, Kun-Qiang
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p. 3073 - 3079,7
(2020/08/20)
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- NAPHTHYRIDINE DERIVATIVES AS INHIBITORS OF HYPOXIA INDUCIBLE FACTOR (HIF) HYDROXYLASE
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The present disclosure relates to novel compounds, methods, and compositions capable of inhibiting HIF hydroxylase enzyme activity, thereby increasing the stability and/or activity of hypoxia inducible factor (HIF).
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Page/Page column 156
(2012/08/27)
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- Cyanuric chloride catalysed rapid conversion of β-ketoesters into β-enaminoesters under mild and solvent-free conditions
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Cyanuric chloride is shown to be an extremely efficient catalyst for the synthesis of β-enaminoesters from β-ketoesters under solvent-free conditions by grinding in a mortar with pestle at 25 °C. A short reaction time, an inexpensive and easily available catalyst, mild reaction conditions and excellent yields of the products are attractive features of this methodology.
- Kamble,Joshi,Atkore
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experimental part
p. 616 - 621
(2012/07/03)
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- Silica sulfuric acid-mediated synthesis of β-enaminones and β-enaminoesters under microwave irradiation
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Silica sulfuric acid, a heterogeneous reagent, has been found to be an efficient catalyst for the synthesis of β-enaminones and β-enaminoesters under microwave irradiation in a microwave reactor within 2 min. The experimental procedure is simple and environment-friendly, and results in excellent yields of the products. Further, the catalyst is recyclable, and the reaction is 60 times faster than the reaction at room temperature. Copyright Taylor & Francis Group, LLC.
- Datta, Bandita,Pasha
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experimental part
p. 171 - 177
(2011/04/22)
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- Stereodefined homopropargyl amines by tandem nucleophilic addition/fragmentation of dihydropyridone triflates
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Dihydropyridone (DHPD) triflates undergo nucleophile-triggered fragmentation to provide homopropargyl amine derivatives, the stereochemistry of which is defined by starting from readily available β-amino esters.
- Tummatorn, Jumreang,Dudley, Gregory B.
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supporting information; experimental part
p. 158 - 160
(2011/03/20)
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