- Active Base Hybrid Organosilica Materials based on Pyrrolidine Builder Units for Fine Chemicals Production
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The catalytic activity of “pyrrolidine type” fragments included or anchored in the mesoporous silica supports or polymeric frameworks have been fully reported for enantioselective transformation. Nevertheless, low attention was focused on their catalytic abilities to perform base-catalyzed reaction. Accordingly, hybrid materials including pyrrolidine fragments in the mesoporous silica supports were prepared following different synthesis methods, such as micellar and fluoride sol-gel routes in absence of structural directing agents. Their great catalytic performance was explored for various base-catalyzed reactions to the formation of C?C bond through Knoevenagel, Claisen-Schmidt and Henry condensations under microwave irradiation. The benefits of microwave irradiation combined with suitable catalytic properties of pyrrolidine hybrid materials with strong base sites and high accessibility to active centers, allowed carrying out successfully base-catalyzed condensation reactions for the production of fine chemicals. Moreover, the hybrid catalyst exhibited high selectivity and good stability over different catalytic cycles contributing to environmental sustainability.
- Llopis, Sebastián,Velty, Alexandra,Díaz, Urbano
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p. 5012 - 5024
(2021/10/19)
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- Diindenopyrazines: Electron-Deficient Arenes
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The syntheses, properties and application of the air-stable electron acceptors, diindenopyrazines 4 a–g are reported demonstrating the introduction of functional aryl groups in the 6- and 12-positions. The targets are accessible on the hundred milligram to gram scale. The structure of the aryl groups in 4 a–g modulates their solubility, redox potentials and optical properties. The introduction of electron-poor aryl groups to the electron-poor diindenopyrazine backbone reduces the electron affinity to ?4 eV, making the compounds attractive as n-semiconductors. A simple organic field-effect transistor of 4 e –without optimization– shows electron transport with a mobility of up to 0.037 cm2 V?1 s?1.
- Brosius, Victor,Bunz, Uwe H. F.,Freudenberg, Jan,Hippchen, Nikolai,Rominger, Frank,Weigold, Svenja
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supporting information
p. 10001 - 10005
(2021/06/07)
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- Dipolar HCP materials as alternatives to DMF solvent for azide-based synthesis
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Hypercrosslinked polymers HCP-DMF and HCP-DMF-SO3H containing abundant and flexible DMF moieties were designed and synthesized. Benefitting from the solvation microenvironment provided by the pseudo-DMF moities, the polar HCPs manifested outstanding performances in the conversions of NaN3 to benzylic azides and 1,2,3-triazoles in EtOH (95%), respectively, avoiding the use of risky DMF and improving the separation processes of the products.
- Bai, Rongxian,Gao, Feng,Gu, Yanlong,Li, Minghao
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supporting information
p. 7499 - 7505
(2021/10/12)
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- Ionic-Liquid Controlled Nitration of Double Bond: Highly Selective Synthesis of Nitrostyrenes and Benzonitriles
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Unprecedented in literature, the conversion of aryl alkenes into β-nitrostyrenes (2) or benzonitriles (3) with sodium nitrite can be governed by an appropriate choice of ionic liquid (IL) medium. A general trend was found for the selectivity of these processes, which depends on the nature of IL, with imidazolium-based ILs, such as [Bmim]Cl, that favor the C–H nitration leading to β-nitrostyrenes, while tetraalkylammonium-based ILs, such as TBAA, privilege the C=C bond cleavage affording benzonitriles. Besides a substrate scope, mechanistic hypotheses were provided on the origin of the different selectivity in the two kinds of ILs, based on their own tunable properties such as polarity, viscosity, and solvent cage effects.
- Casiello, Michele,Caputo, Daniela,Fusco, Caterina,Cotugno, Pietro,Rizzi, Vito,Dell'Anna, Maria Michela,D'Accolti, Lucia,Nacci, Angelo
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supporting information
p. 6012 - 6018
(2020/08/24)
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- A diversity-oriented synthesis of polyheterocycles: Via the cyclocondensation of azomethine imine
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Pd-Catalyzed sequential reactions to afford skeletally diverse molecules are described. The reaction involved azomethine imine formation and a cyclocondensation reaction as individual steps. The methodology provides excellent regio- and stereocontrol. Skeletal diversity was ensured by changing the electrophilic counterpart of azomethine imine. Due to its broader diversity and complexity, the DOS methodology is likely to benefit drug discovery and development in the future.
- Ansari, Arshad J.,Pathare, Ramdas S.,Kumawat, Anita,Maurya, Antim K.,Verma, Sarika,Agnihotri, Vijai K.,Joshi, Rahul,Metre, Ramesh K.,Sharon, Ashoke,Pardasani,Sawant, Devesh M.
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supporting information
p. 13721 - 13724
(2019/09/16)
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- Substrate promiscuity of ortho-naphthoquinone catalyst: Catalytic aerobic amine oxidation protocols to deaminative cross-coupling and n-nitrosation
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ortho-Naphthoquinone-based organocatalysts have been identified as versatile aerobic oxidation catalysts. Primary amines were readily cross-coupled with primary nitroalkanes via deaminative pathway to give nitroalkene derivatives in good to excellent yields. Secondary and tertiary amines were inert to ortho-naphthoquinone catalysts; however, secondary nitroalkanes were readily converted by ortho-naphthoquinone catalysts to the corresponding nitrite species that in situ oxidized the amines to the corresponding N-nitroso compounds. Without using harsh oxidants in a stoichiometric amount, the present catalytic aerobic oxidation protocol utilizes the substrate promiscuity feature to provide a facile access to amine oxidation products under mild reaction conditions.
- Kim, Hun Young,Oh, Kyungsoo,Si, Tengda
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p. 9216 - 9221
(2019/10/08)
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- A Deprotonation Approach to the Unprecedented Amino-Trimethylenemethane Chemistry: Regio-, Diastereo-, and Enantioselective Synthesis of Complex Amino Cycles
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The first realization of the amino-trimethylenemethane chemistry is reported using a deprotonation strategy to simplify the synthesis of the amino-trimethylenemethane donor in two steps from commercial and inexpensive materials. A broad scope of cycloaddition acceptors (seven different classes) participated in the chemistry, chemo-, regio-, diastereo-, and enantioselectively generating various types of highly valuable complex amino cycles. Multiple derivatization reactions that further elaborated the initial amino cycles were performed without isolation of the crude product. Ultimately, we applied the amino-trimethylenemethane chemistry to synthesize a potential pharmaceutical in 8 linear steps and 7.5 % overall yield, which previously was achieved in 18 linear steps and 0.6 % overall yield.
- Trost, Barry M.,Wang, Youliang
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supporting information
p. 11025 - 11029
(2018/07/30)
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- Catalyst- and Substituent-Controlled Switching of Chemoselectivity for the Enantioselective Synthesis of Fully Substituted Cyclobutane Derivatives via 2 + 2 Annulation of Vinylogous Ketone Enolates and Nitroalkene
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The first regioselective, diastereoselective, and enantioselective organocatalyzed Michael-Michael cascade of vinylogous ketone enolates and nitroalkenes for the construction of fully substituted cyclobutanes is achieved by the deployment of the appropriate chiral squaramide catalyst and the pertinent substituent on the substrate. The domino reaction provided cyclobutanes with four contiguous stereocenters, including a quaternary center in good yields with diastereomeric ratio of >20:1 and with enantioselectivities of mostly up to 98% enantiomeric excess (ee). The structures and the absolute configurations of the adducts were confirmed by single-crystal X-ray crystallographic analyses of the appropriate products.
- Akula, Pavan Sudheer,Hong, Bor-Cherng,Lee, Gene-Hsiang
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supporting information
p. 7835 - 7839
(2019/01/04)
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- Synthesis, antiproliferative and pro-apoptotic effects of nitrostyrenes and related compounds in Burkitt’s lymphoma
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Background: Cancers of the lymphatic cells (lymphomas) account for approximately 12% of malignant diseases worldwide. The nitrostyrene scaffold is identified as a lead target structure for the development of particularly effective compounds targeting Burkitt’s lymphoma (BL). Objectives: The aims of the curent study were to synthesise a panel of nitrostyrene compounds and to evaluate their activity in Burkitt’s lymphoma (BL). Methods: A panel of structurally varied compounds were designed and synthesised using Henry Knoevenagel condensation reactions. Single crystal X-Ray analysis confirmed the E configuration for six examples of these novel structures. A number of nitrostyrene-related compounds were also investigated including 1,3-bis(aryl)-2-nitropropenes together with heterocyclic scaffolds containing the nitrovinyl pharmacophore such as 3-nitro-2-phenyl-2H-chromenes. The antiproliferative activities of the compounds were evaluated using the BL cell lines EBV- MUTU-1 and EBV+ DG-75 (chemoresistant) to establish preliminary structure-activity relationships. Results: Lead compounds with optimized nitrostyrene scaffolds and 3-nitro-2-phenyl-2Hchromene structures were successfully established with typical IC50 values of 0.45 μM and 0.47 μM in MUTU-1 cells and 1.41 μM and 1.92 μM, respectively, in DG-75 cells. The mechanism of cell death was identified as apoptotic and the lead compound was found to elicit comparable apoptotic effects to Taxol in Burkitt’s lymphoma cell lines MUTU-1 and DG-75. Conclusion: This class of pharmaceutically active compounds with potential for the treatment of Burkitt’s lymphoma suggest a potential role for nitrostyrene based agents in chemotherapy.
- Byrne, Andrew J.,Bright, Sandra A.,Fayne, Darren,McKeown, James P.,McCabe, Thomas,Twamley, Brendan,Williams, Clive,Meegan, Mary J.
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p. 181 - 199
(2018/03/13)
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- Electronic effect of substituents on anilines favors 1,4-addition to: Trans -β-nitrostyrenes: Access to N -substituted 3-arylindoles and 3-arylindoles
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A simple and an efficient method for the regioselective synthesis of N-alkyl/aryl/H 3-arylindole derivatives from N-substituted anilines and trans-β-nitrostyrenes has been described using 10 mol% of bismuth(iii) triflate as a catalyst in acetonitrile at 80 °C. The present protocol profits from the formation of new C-C and C-N bonds, broad substrate scope and moderate to good yields.
- Gattu, Radhakrishna,Bhattacharjee, Suchandra,Mahato, Karuna,Khan, Abu T.
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supporting information
p. 3760 - 3770
(2018/05/30)
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- Method for synthesizing nitroolefin compound
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The invention relates to a method for synthesizing an organic compound. The method is used for solving the problem of current synthesis of nitroolefin compounds that reaction byproducts are numerous,raw materials are expensive, and some methods are relatively troublesome in aftertreatment. The invention provides a method for preparing a nitroolefin compound. The nitroolefin compound is prepared through subjecting a cinnamyl aldehyde compound, which serves as a starting material, to a reaction with a nitrate and a solvent for 1 to 24 hours at the temperature of 25 DEG C to 150 DEG C. A methodfor direct nitration by using a cheap nitrate is achieved. The method is a new route for synthesizing the nitroolefin compound.
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Paragraph 0082-0084
(2018/03/26)
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- Discovery of a PCAF Bromodomain Chemical Probe
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The p300/CBP-associated factor (PCAF) and related GCN5 bromodomain-containing lysine acetyl transferases are members of subfamily I of the bromodomain phylogenetic tree. Iterative cycles of rational inhibitor design and biophysical characterization led to the discovery of the triazolopthalazine-based L-45 (dubbed L-Moses) as the first potent, selective, and cell-active PCAF bromodomain (Brd) inhibitor. Synthesis from readily available (1R,2S)-(?)-norephedrine furnished L-45 in enantiopure form. L-45 was shown to disrupt PCAF-Brd histone H3.3 interaction in cells using a nanoBRET assay, and a co-crystal structure of L-45 with the homologous Brd PfGCN5 from Plasmodium falciparum rationalizes the high selectivity for PCAF and GCN5 bromodomains. Compound L-45 shows no observable cytotoxicity in peripheral blood mononuclear cells (PBMC), good cell-permeability, and metabolic stability in human and mouse liver microsomes, supporting its potential for in vivo use.
- Moustakim, Moses,Clark, Peter G. K.,Trulli, Laura,Fuentes de Arriba, Angel L.,Ehebauer, Matthias T.,Chaikuad, Apirat,Murphy, Emma J.,Mendez-Johnson, Jacqui,Daniels, Danette,Hou, Chun-Feng D.,Lin, Yu-Hui,Walker, John R.,Hui, Raymond,Yang, Hongbing,Dorrell, Lucy,Rogers, Catherine M.,Monteiro, Octovia P.,Fedorov, Oleg,Huber, Kilian V. M.,Knapp, Stefan,Heer, Jag,Dixon, Darren J.,Brennan, Paul E.
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supporting information
p. 827 - 831
(2017/01/14)
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- Catalytic asymmetric Tamura cycloadditions involving nitroalkenes
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The first examples of asymmetric Tamura cycloaddition reactions involving singly activated alkenes are reported. Homophthalic anhydride reacts with α-methyl nitrosytrenes in the presence of an alkaloid-based catalyst to generate fused bicyclic aromatic ketone products with three new stereocentres (which are susceptible to subsequent equilibration) in 12-99% ee. An unusual equilibration process which occurs in methanolic medium in the absence of a recognisable base via proton transfer at the α-carbon of an ester was investigated experimentally and computationally.
- Manoni, Francesco,Farid, Umar,Trujillo, Cristina,Connon, Stephen J.
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p. 1463 - 1474
(2017/02/15)
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- In order to iodide is one pot synthesis nitryl source α, β - unsaturated nitro olefin derivatives (by machine translation)
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The present invention discloses a one-pot synthesis nitryl source iodide is α, β - unsaturated nitro olefin derivatives, vinyl compounds containing four aryl ferrous (III), iodide and tertiary-butyl hydrogen peroxide in acetonitrile solution system a pot of reaction, generating α, β - unsaturated nitro olefin derivatives; the method to achieve the under mild reaction conditions, high yield with high stereo selectivity of the E synthesis of α, β - unsaturated nitro olefin. (by machine translation)
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Paragraph 0122-0125; 0135-0137
(2017/09/01)
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- Α, β - unsaturated nitro olefin derivative synthesis method (by machine translation)
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The invention discloses a α, β - unsaturated nitro olefin derivative synthesis method, vinyl compounds containing four aryl ferrous (III), ammonium halide and tertiary-butyl hydrogen peroxide in the system of the one-pot reaction, generating α, β - unsaturated nitro olefin derivatives; the method to achieve the under mild reaction conditions, high yield with high stereo selectivity of the E synthesis of α, β - unsaturated nitro olefin. (by machine translation)
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Paragraph 0027; 0034; 0124; 0126; 0136; 0137; 0138
(2017/09/05)
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- Insights into the diastereoselective control in the sulfa-Michael addition of thiols to nitroalkenes: Stereoelectronic effect in the cyclic chelated transition state
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The diastereoselective control in the sulfa-Michael addition of nitroalkenes and lithium thiolates followed by protonation was investigated. Lithium thiolates first added to nitroalkenes to afford cyclic lithium-chelated nitronates. The subsequent kinetic protonation of nitronates was proved to be the stereochemical determinant through the chelate-controlled six-membered half-chair transition state bearing two approximately 1,2-diaxial substituents due to stereoelectronic effect control. The stereoelectronic effect in the cyclic chelated transition state was probed and verified by tuning the steric bulkiness of the corresponding substituents. The reaction involving 1-nitrocyclohexene provided perfect support for the proposed diastereoselective control model. The current investigation provided not only comprehensive insights into the diastereoselective control in the sulfa-Michael addition of nitroalkenes and thiolates, but also an important role of the stereoelectronic effect in certain organic reactions involving cyclic chelate transition states.
- Wang, Jiandong,Li, Pingfan,Yang, Zhanhui,Chen, Ning,Xu, Jiaxi
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p. 370 - 378
(2015/12/31)
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- K2S2O8-mediated nitration of alkenes with NaNO2 and 2,2,6,6-tetramethylpiperidine-1-oxyl: Stereoselective synthesis of (E)-nitroalkenes
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A transition-metal-free nitration of alkenes with NaNO2 in the presence of K2S2O8 and 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) is developed. The transformation exhibits a broad substrate scope and good functional group tolerance, thus providing a new and expedient protocol for stereoselective synthesis of (E)-nitroalkenes with moderate to good yields. Moreover, the nitration processes of (E)- and (Z)-stilbene are also studied: even though the proportion of substrates is different, the E/Z ratio of the products is basically the same. Based upon experimental observations, a possible reaction mechanism is proposed.
- Zhao, An,Jiang, Qing,Jia, Jing,Xu, Bin,Liu, Yufeng,Zhang, Mingzhong,Liu, Qiang,Luo, Weiping,Guo, Cancheng
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supporting information
p. 80 - 84
(2015/12/23)
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- Nitration-Oximization of Styrene Derivatives with tert-Butyl Nitrite: Synthesis of α-Nitrooximes
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A highly efficient method for direct nitration-oximization of styrene derivatives using tert-butyl nitrite (t-BuONO) in DMSO was developed. The present method offers a convenient and practical approach for the synthesis of α-nitrooximes in moderate to high yields. The salient features entail mild reaction conditions, metal-free reagent, environmentally benign solvent and simple experimental procedure.
- Chumnanvej, Napasawan,Katrun, Praewpan,Pohmakotr, Manat,Reutrakul, Vichai,Soorukram, Darunee,Kuhakarn, Chutima
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p. 830 - 838
(2016/09/03)
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- Cathodic hydrodimerization of nitroolefins
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Nitroalkenes are easily accessible in high variety by condensation of aldehydes with aliphatic nitroalkanes. They belong to the group of activated alkenes that can be hydrodimerized by cathodic reduction. There are many olefins with different electron withdrawing groups used for cathodic hydrodimerization, but not much is known about the behaviour of the nitro group. Synthetic applications of this group could profit from the easy access to nitroolefins in large variety, the C-C bond formation with the introduction of two nitro groups in a 1,4-distance and the conversions of the nitro group by reduction to oximes and amines, the conversion into aldehydes and ketones via the Nef reaction and base catalyzed condensations at the acidic CH bond. Eight 1-aryl-2-nitro-1-propenes have been electrolyzed in an undivided electrolysis cell to afford 2,5-dinitro-3,4-diaryl hexanes in high yield. The 4-methoxy-, 4-trifluoromethyl-, 2-chloro- and 2,6-difluorophenyl group and furthermore the 2-furyl and 2-pyrrolyl group have been applied. The reaction is chemoselective as only the double bond but not the nitro group undergoes reaction, is regioselective as a β,β-coupling with regard to the nitro group and forms preferentially two out of six possible diastereomers as major products.
- Wessling, Michael,Sch?fer, Hans J.
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supporting information
p. 1163 - 1174
(2015/08/18)
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- Hierarchical high-silica zeolites as superior base catalysts
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For more than four decades, the design of zeolite base catalysts has relied on the application of aluminium-rich frameworks exchanged with alkali metal cations (preferably Cs+). However, moderate activity associated with access and diffusion limitations, and high manufacturing costs associated with high caesium content (typically over 30%) have hampered their industrial implementation so far. Herein, we have discovered that high-silica USY zeolites outperform their Al-rich counterparts in a variety of base-catalysed reactions of relevance in the fine chemical industry, as well as in the upgrading of biofuels. The benefits of this class of materials are amplified upon the alleviation of diffusion constraints through the introduction of a network of intracrystalline mesopores by post-synthetic modification. For example, the resulting cation-free hierarchical USY provides an up to 30-fold Knoevenagel condensation activity compared to the benchmark Cs-X, and similar observations were made upon application in liquid-phase (nitro)aldol reactions. Moreover, in the gas-phase aldol condensation of propanal, high-silica zeolites provide superior activity, selectivity, and lifetime compared to caesium-containing zeolites and even a strong solid base such as MgO. We decouple the complex interplay between mesoporosity and intrinsic zeolitic properties such as crystallinity, and quantify the increase in catalyst effectiveness upon hierarchical structuring as a function of reactant size. The obtained results are a major step to resolve the drawbacks of zeolites catalysis and thereby revitalise their potential for industrial application.
- Keller, Tobias C.,Isabettini, Stephane,Verboekend, Danny,Rodrigues, Elodie G.,Perez-Ramirez, Javier
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p. 677 - 684
(2014/01/17)
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- Enantioselective hydrogenation of α,β-disubstituted nitroalkenes
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The first highly chemo- and enantioselective hydrogenation of α,β-disubstituted nitroalkenes was accomplished with rhodium/JosiPhos-J2 as a catalyst, with the yield and enantioselectivity of up to 95% and 94%, respectively. The α-chiral nitroalkanes will provide an entry to valuable chiral amphetamines which are otherwise not so easily accessed. This journal is the Partner Organisations 2014.
- Li, Shengkun,Huang, Kexuan,Zhang, Xumu
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supporting information
p. 8878 - 8881
(2014/08/05)
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- Oxone/KI-Mediated Nitration of Alkenes and Alkynes: Synthesis of Nitro- and β-Iodonitro-Substituted Alkenes
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Oxone (2KHSO5·KHSO4·K2SO4) was used to promote the nitration of alkenes and alkynes with sodium nitrite (NaNO2) and potassium iodide (KI). This stable, easy-to-handle, and environmentally benign oxidant was used under mild conditions (room temperature) and provided short reaction times. Styrene derivatives that did not contain electron-donating groups afforded the corresponding nitro alkenes in moderate to good yields, whereas aliphatic alkenes and electron-deficient alkenes were not good substrates. Under similar reaction conditions, aryl alkynes yielded β-iodonitro alkenes. Oxone (2KHSO5·KHSO4·K2SO4) was used to promote the reactions of alkenes and alkynes with sodium nitrite (NaNO2) and potassium iodide (KI) to afford the corresponding nitro and β-iodonitro-substituted alkenes, respectively, in moderate to good yields.
- Hlekhlai, Sornsiri,Samakkanad, Natthapol,Sawangphon, Tassaporn,Pohmakotr, Manat,Reutrakul, Vichai,Soorukram, Darunee,Jaipetch, Thaworn,Kuhakarn, Chutima
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p. 7433 - 7442
(2016/02/19)
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- Convenient synthesis of α-nitrooximes mediated by OXONE
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A novel OXONE mediated direct difunctionalization of alkenes with NaNO2 in aqueous acetonitrile for the synthesis of α-nitrooximes was developed. The α-nitrooximes were readily prepared in moderate to high yields at room temperature under mild reaction conditions. The present protocol offers an easy and environmentally benign approach to access various α-nitrooximes derived from styrene derivatives.
- Chumnanvej, Napasawan,Samakkanad, Natthapol,Pohmakotr, Manat,Reutrakul, Vichai,Jaipetch, Thaworn,Soorukram, Darunee,Kuhakarn, Chutima
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p. 59726 - 59732
(2015/02/19)
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- Iron-catalyzed tandem one-pot addition and cyclization of the blaise reaction intermediate and nitroolefins: Synthesis of substituted NH-pyrroles from nitriles
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The iron-catalyzed addition and cyclization of the Blaise reaction intermediate and nitroolefins to synthesize highly functionalized NH-pyrroles in a tandem one-pot manner from nitriles has been developed. This reaction shows good functional group tolerance and affords a broad spectrum of substituted NH-pyrroles in good yields. Copyright
- Zhao, Mi-Na,Liang, Hao,Ren, Zhi-Hui,Guan, Zheng-Hui
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supporting information
p. 221 - 226
(2013/03/13)
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- Highly enantioselective reduction of α-methylated nitroalkenes
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Highly selective: The reduction of α-methyl-substituted nitroalkenes succeeds in a highly enantioselective fashion with an ene reductase from Gluconobacter oxydans. Under optimized reaction conditions the desired nitroalkanes are formed with enantiomeric excesses of up to 95% in these biotransformations. Copyright
- Burda, Edyta,Re?, Tina,Winkler, Till,Giese, Carolin,Kostrov, Xenia,Huber, Tobias,Hummel, Werner,Gr?ger, Harald
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supporting information
p. 9323 - 9326
(2013/09/12)
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- Selective conversion of nitroalcohols to nitroolefins over sulfonic acid functionalized mesoporous SBA-15 material
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Highly ordered 2D-hexagonal mesoporous SBA-15 has been synthesized by using triblock copolymer as template and its surface has been functionalized by 3-propylsulfonic acid group via post-synthetic grafting with 3-mercaptopropyltrimethoxy silane. A variety of α,β-substituted nitroalcohols are converted to their corresponding nitroolefins under mild reaction conditions using this 3-propylsulfonic acid-functionalized SBA-15 material. Nitroalcohols with open-chain, cyclic, and heterocyclic substituents at the α-position are smoothly converted into their corresponding nitroolefins in high yields over this solid acid catalyst. Propylsulfonic acid functionalized SBA-15 materials are found to be more efficient catalysts than microporous zeolites under similar reaction conditions.
- Sasidharan, Manickam,Bhaumik, Asim
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- One-pot solid phase synthesis of (E)-nitroalkenes
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An efficient one-pot protocol for the synthesis of (E)-nitroalkenes by reaction of aldehydes and nitroalkanes in the presence of polymer-bound triphenylphosphine, iodine and imidazole is described. Although the reaction works with similar efficiency with triphenylphosphine and its polymer-bound version, easy removal of the unwanted polymer-bound triphenylphosphine oxide and its recovery as triphenylphosphine provide the edge for practical application of the method.
- Rokhum, Lalthazuala,Bez, Ghanashyam
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p. 5500 - 5504
(2013/09/23)
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- A predictably selective nitration of olefin with Fe(NO3) 3 and TEMPO
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Ferric nitrate with catalytic TEMPO has been identified as a useful reagent for regio- and stereoselective nitration of a wide variety of aromatic, aliphatic, and heteroaromatic olefins. This reaction provided nitroolefins in preparatively useful yields with excellent E-selectivity. Due to its mild nature and operational simplicity, the present protocol is expected to find application in synthetic setup.
- Naveen, Togati,Maity, Soham,Sharma, Upendra,Maiti, Debabrata
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p. 5949 - 5954
(2013/07/26)
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- Synthesis of nitroalkenes involving a cooperative catalytic action of iron(III) and piperidine: A one-pot synthetic strategy to 3-alkylindoles, 2H-chromenes and N-arylpyrrole
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An efficient and simple strategy has been developed to synthesize various substituted nitroalkenes involving a cooperative catalytic system of FeCl 3 and piperidine. This dual catalytic protocol simultaneously activates both electrophile and nucleophile and works under mild reaction conditions so that many sensitive functional groups were tolerated. Moreover, this cooperative catalytic reaction is also suitable for various one-pot reactions involving nitroalkenes such as, 2H-chromenes, N-arylpyrrole and Michael reaction with indole. Notably, this method is low-cost, efficient and environmentally friendly. Copyright
- Jalal, Swapnadeep,Sarkar, Soumen,Bera, Krishnendu,Maiti, Sukhendu,Jana, Umasish
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supporting information
p. 4823 - 4828
(2013/08/23)
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- Design of phosphorus ligands with deep chiral pockets: Practical Synthesis of chiral β-arylamines by asymmetric hydrogenation
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WingPhos, a C2-symmetric bisphosphorus ligand with a deep and well-defined chiral pocket was developed. It has shown high efficiency in the rhodium-catalyzed asymmetric hydrogenation of (E)-β-aryl-N-acetyl enamides, cyclic β-aryl enamides, and heterocyclic β-aryl enamides. A series of chiral β-arylisopropylamines, 2-aminotetralines, and 3-aminochromans can be synthesized with excellent ee values (nbd=3,5-norbornadiene; TON=turnover number). Copyright
- Liu, Guodu,Liu, Xiangqian,Cai, Zhihua,Jiao, Guangjun,Xu, Guangqing,Tang, Wenjun
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supporting information
p. 4235 - 4238
(2013/05/08)
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- Dynamic kinetic asymmetric ring-opening/reductive amination sequence of racemic nitroepoxides with chiral amines: Enantioselective synthesis of chiral vicinal diamines
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We report a highly diastereoselective synthesis of vicinal diamines by the treatment of nitroepoxides with primary amines and then a reducing agent. When using a chiral primary amine, racemic nitroepoxides are transformed into chiral diamines as a single enantiomers (>95:5 er) through a dynamic kinetic asymmetric transformation (DYKAT). The overall process is a one-pot procedure combining the exposure of nitroepoxides to chiral amines to afford diastereomeric mixtures of aminoimines and subsequent stereoselective imine reduction.
- Agut, Juan,Vidal, Andreu,Rodríguez, Santiago,González, Florenci V.
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p. 5717 - 5722
(2013/07/25)
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- Synthesis of (E)-nitroolefins via decarboxylative nitration using t-butylnitrite (t-BuONO) and TEMPO
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Nitroolefins are usually synthesized using the Henry reaction. Here we report an alternative metal-free decarboxylative nitration protocol for the preparation of the nitroolefins from α,β-unsaturated carboxylic acids using t-butylnitrite (t-BuONO) and TEMPO. α,β-Unsaturated carboxylic acids bearing β-aromatic and β-heteroaromatic substituents gave (E)-nitroolefins exclusively under mild conditions. A radical based pathway has been proposed for this decarboxylative nitration reaction. The Royal Society of Chemistry 2013.
- Manna, Srimanta,Jana, Sandipan,Saboo, Tapish,Maji, Arun,Maiti, Debabrata
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supporting information
p. 5286 - 5288
(2013/06/27)
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- Efficient and stereoselective nitration of mono- and disubstituted olefins with AgNO2 and TEMPO
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Nitroolefin is a common and versatile reagent. Its synthesis from olefin is generally limited by the formation of mixture of cis and trans compounds. Here we report that silver nitrite (AgNO2) along with TEMPO can promote the regio- and stereoselective nitration of a broad range of olefins. This work discloses a new and efficient approach wherein starting from olefin, nitroalkane radical formation and subsequent transformations lead to the desired nitroolefin in a stereoselective manner.
- Maity, Soham,Manna, Srimanta,Rana, Sujoy,Naveen, Togati,Mallick, Arijit,Maiti, Debabrata
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supporting information
p. 3355 - 3358
(2013/04/10)
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- Synthesis and characterization of Piperidine-4-carboxylic acid functionalized Fe3O4 nanoparticles as a magnetic catalyst for Knoevenagel reaction
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Piperidine-4-carboxylic acid (PPCA) functionalized Fe3O 4 nanoparticles as a novel organic-inorganic hybrid heterogeneous catalyst was fabricated and characterized by XRD, FT-IR, TGA, TEM and VSM techniques. Composition was determined as Fe3O4, while particles were observed to have spherical morphology. Size estimations using X-ray line profile fitting (10 nm), TEM (11 nm) and magnetization fitting (9 nm) agree well, revealing nearly single crystalline character of Fe 3O4 nanoparticles. Magnetization measurements reveal that PPCA functionalized Fe3O4 NPs have superparamagnetic features, namely immeasurable coercivity and absence of saturation. Small coercivity is established at low temperatures. The catalytic activity of Fe 3O4-PPCA was probed through one-pot synthesis of nitro alkenes through Knoevenagel reaction in CH2Cl2 at room temperature. The heterogeneous catalyst showed very high conversion rates (97%) and could be recovered easily and reused many times without significant loss of its catalytic activity.
- Karaoglu,Baykal,?enel,S?zeri,Toprak
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experimental part
p. 2480 - 2486
(2012/10/08)
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- Exploring nitrostyrene as a scaffold for a new class a of monoamine oxidase inhibitors
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With the ultimate purpose of finding out the structural features that are relevant for MAO inhibitory activity and selectivity towards MAO-B isoform, a series of compounds encompassing a β-nitrostyrene moiety was designed and the in vitro inhibitory activity was evaluated. In the present work, we report the synthesis and the pharmacological evaluation of a series of functionalized derivatives of β-methyl-β-nitrostyrene with distinct substitution patterns in the phenyl ring, namely hydroxyl, methoxy, benzyloxy and methylenedioxy. All the studied compounds were substituted in meta and para positions of the phenyl ring related to the nitrovinyl side chain. The synthesized compounds were evaluated towards both human MAO isoforms, displaying some of them activities in the low micromolar range. Particularly compound 6 (a methylenedioxy derivative) exhibits high potency and selectivity towards MAO-B.
- Reis, Joana,Oliveira, Catarina,Milhazes, Nuno,Vi?a, Dolores,Borges, Fernanda
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p. 958 - 961
(2013/02/23)
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- Enzymatic enantiomeric resolution of phenylethylamines structurally related to amphetamine
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Both enantiomers of several phenylethylamines, structurally related to amphetamine, have been prepared in good yields and excellent enantiomeric purity by enzymatic kinetic resolution using CAL-B and ethyl methoxyacetate as the acyl donor. In the case of the 4-hydroxyderivative of amphetamine (compound 4i), the S enantiomer racemized possibly in a dynamic kinetic resolution (DKR) under the enzymatic conditions used. The Royal Society of Chemistry 2011.
- Munoz, Lourdes,Rodriguez, Anna M.,Rosell, Gloria,Bosch, M. Pilar,Guerrero, Angel
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experimental part
p. 8171 - 8177
(2012/01/04)
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- NOVEL FUSED PYRIDAZINE DERIVATIVES
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The present invention relates to novel fused pyridazine compounds, their pharmaceutically acceptable salts, and their isomers, stereoisomers, conformers, tautomers, polymorphs, hydrates and solvates. The present invention also encompasses pharmaceutically acceptable compositions of said compounds and process for preparing novel compounds. The invention further relates to the use of the above-mentioned compounds for the preparation of medicament for use as pharmaceuticals.
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Page/Page column 73
(2011/05/06)
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- Ambiphilic dual activation role of a task-specific ionic liquid: 2-hydroxyethylammonium formate as a recyclable promoter and medium for the green synthesis of β-nitrostyrenes
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A cost-effective task-specific ionic liquid, 2-hydroxyethylammonium formate, efficiently promotes the condensation of nitroalkanes with various aldehydes to produce β-nitrostyrenes in high to excellent yields at room temperature. This reaction does not involve any hazardous organic solvent and toxic catalyst. The ionic liquid is recovered and recycled for subsequent reactions. In addition, a novel mechanism has been proposed invoking ambiphilic dual activation influence of the ionic liquid.
- Alizadeh, Abdolhamid,Khodaei, Mohammad M.,Eshghi, Ali
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scheme or table
p. 8295 - 8298
(2011/03/17)
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- δ13C and δ13H isotope ratios in amphetamine synthesized from benzaldehyde and nitroethane
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Previous work in these laboratories and by Butzenlechner et al. and Culp et al. has demonstrated that the δ2H isotope value of industrial benzaldehyde produced by the catalytic oxidation of toluene is profoundly positive, usually in the range +300% to +500%. Synthetic routes leading to amphetamine, methylamphetamine or their precursors and commencing with such benzaldehyde may be expected to exhibit unusually positive δ2H values. Results are presented for δ13C and δ2H isotope values of 1-phenyl-2-nitropropene synthesized from an industrial source of benzaldehyde, having a positive δ2H isotope value, by a Knoevenagel condensation with nitroethane. Results are also presented for δ13C and δ2H isotope values for amphetamine prepared from the resulting 1-phenyl-2-nitropropene. The values obtained were compared with δ13C and δ2H isotope values obtained for an amphetamine sample prepared using a synthetic route that did not involve benzaldehyde. Finally, results are presented for samples of benzaldehyde, 1-phenyl-2-nitropropene and amphetamine that had been seized at a clandestine amphetamine laboratory.
- Collins, Michael,Salouros, Helen,Cawley, Adam T.,Robertson, James,Heagney, Aaron C.,Arenas-Queralt, Andrea
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experimental part
p. 1653 - 1658
(2011/10/13)
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- Henry reaction catalyzed by aminopropylated nanosilica
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The Henry reaction was catalyzed by 0.01 equiv of aminopropylated nanosilica particles (nano-NAP) in refiuxing nitroalkanes to provide nitrostyrenes in good yields. The catalyst could be recycled up to three times in 76% average yield. Copyright
- Hagiwara, Hisahiro,Sekifuji, Masayoshi,Tsubokawa, Norio,Hoshi, Takashi,Suzuki, Toshio
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scheme or table
p. 790 - 791
(2010/03/04)
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- Michael addition initiated carbocyclization sequences with nitroolefins for the stereoselective synthesis of functionalized heterocyclic and carbocyclic systems
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The synthesis of various heterocycles and carbocycles (tetrahydrofurans, pyrrolidines, cyclopentanes) has been achieved by using new and efficient ionic addition/cyclization sequences. Nitroolefins play an important role in the Michael addition induced ring-closing reactions (MIRC) reported in the present article, with various substituted alcohols, amines, Grignard reactants, or malonate derivatives acting as the nucleophile partner. The optimized cascade reactions were high yielding in most cases and highly stereoselective, creating up to three stereogenic centers starting from achiral substrates.
- Dumez, Estelle,Durand, Anne-Catherine,Guillaume, Martial,Roger, Pierre-Yves,Faure, Robert,Pons, Jean-Marc,Herbette, Gaetan,Dulcere, Jean-Pierre,Bonne, Damien,Rodriguez, Jean
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body text
p. 12470 - 12488
(2010/06/11)
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- Selective nitroaldol condensations over heterogeneous catalysts in the presence of supercritical carbon dioxide
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(Chemical Equation Presented) At 40-60°C, in the presence of heterogeneous catalysts based on Al2O3, supercritical carbon dioxide not only acts as a good solvent for the reaction of aromatic and aliphatic aldehydes with 1-nitroalkanes but, most importantly, it also allows the selectivity to be tuned between the competitive formation of β-nitroalcohols and nitroalkenes (from the Henry reaction and the nitroaldol condensation, respectively). In particular, when the pressure (and the density) of the supercritical phase is enhanced from 80 to 140 bar, the nitroalkene's selectivity increases, on average, from ～60 to >90%. Experiments show that, in the same pressure range, a steep increase of the concentration profiles of reactant aldehydes takes place. By contrast, under solvent-free conditions, the reaction usually proceeds with a higher conversion, but nitroalkanols are the major products.
- Ballini, Roberto,Noe, Marco,Perosa, Alvise,Selva, Maurizio
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supporting information; experimental part
p. 8520 - 8528
(2009/04/05)
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- Acid-base bifunctional catalysis of silica-alumina-supported organic amines for carbon-carbon bond-forming reactions
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Acid-base bifunctional heterogeneous catalysts were prepared by the reaction of an acidic silica-alumina (SA) surface with silane-coupling reagents possessing amino functional groups. The obtained SA-supported amines (SA-NR 2) were characterized by solid-state 13C and 29Si NMR spectroscopy, FT-IR spectroscopy, and elemental analysis. The solid-state NMR spectra revealed that the amines were immobilized by acid-base interactions at the SA surface. The interactions between the surface acidic sites and the immobilized basic amines were weaker than the interactions between the SA and free amines. The catalytic performances of the SA-NR 2 catalysts for various carbon-carbon bond-forming reactions, such as cyano-ethoxycarbonylation, the Michael reaction, and the nitro-aldol reaction, were investigated and compared with those of homogeneous and other heterogeneous catalysts. The SA-NR2 catalysts showed much higher catalytic activities for the carbon-carbon bond-forming reactions than heterogeneous amine catalysts using other supports, such as SiO2 and Al 2O3. On the other hand, homogeneous amines hardly promoted these reactions under similar reaction conditions, and the catalytic behavior of SA-NR2 was also different from that of MgO, which was employed as a typical heterogeneous base. An acid-base dual-activation mechanism for the carbon-carbon bond-forming reactions is proposed.
- Motokura, Ken,Tomita, Mitsuru,Tada, Mizuki,Iwasawa, Yasuhiro
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experimental part
p. 4017 - 4027
(2009/05/07)
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- Rational design of sugar-based-surfactant combined catalysts for promoting glycerol as a solvent
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The use of glycerol as a solvent for environmentally friendly organic reactions has been demonstrated. It was observed that the surfactant combined catalysts (SCCs) with glycerol can enhance the diffusion of organic substrate in the glycerol. The study found that micellar catalysis in glycerol form a unstable emulsions. The study also investigated the reaction of 1,2-epoxydodecane with dodecanoic acid at at temperature of 110°C in glycerol. Diethoanolamine with dodecanoic acid can be used as a phase-transfer agent which can accelerate the diffusion of organic substrate in the glycerol. The study also concluded that the surfactant need to be use with a catalysis to use glycerol as solvent for the improved diffusion of organic compounds. The study used renewable resources to provide an eco-friendly environment during all reactions.
- Karam, Ayman,Villandier, Nicolas,Delample, Mathieu,Koerkamp, Carmen Klein,Douliez, Jean-Paul,Granet, Robert,Krausz, Pierre,Barrault, Joel,Jerome, Francois
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supporting information; experimental part
p. 10196 - 10200
(2009/10/16)
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- Highly enantioselective reduction of β,β-disubstituted aromatic nitroalkenes catalyzed by Clostridium sporogenes
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(Chemical Equation Presented) This is the first report of the use of Clostridium sporogenes extracts for enantioselective reduction of C=C double bonds of β,β-disubstituted (1) and α,β-disubstituted nitroalkenes (3). Crude enzyme preparations reduced aryl derivatives 1a-e and 1h, in 35-86% yield with ≥97% ee. Reduction of (E)- and (Z)-isomers of 1c gave the same enantiomer of 2c (≥99% ee). In contrast, α,β- disubstituted nitroalkene 3a was a poor substrate, yielding (S)-4a in low yield (10-20%), and the ee (30-70% ee) depended on NADH concentration. An efficient synthesis of a library of nitroalkenes 1 is described.
- Fryszkowska, Anna,Fisher, Karl,Gardiner, John M.,Stephens, Gill M.
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p. 4295 - 4298
(2008/12/20)
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- An efficient synthesis of (E)-nitroalkenes catalyzed by recoverable diamino-functionalized mesostructured polymers
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A clean, efficient, and simple method has been developed for synthesis of (E)-nitroalkenes using FDU-ED as an efficient catalyst. The reactions proceeded with moderate to high yields (60-96%) under mild conditions. The catalyst FDU-ED is recyclable and can be reused more than seven times without significant loss of activity and selectivity.
- Yan, Shaoyu,Gao, Yuan,Xing, Rong,Shen, Yali,Liu, Yueming,Wu, Peng,Wu, Haihong
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p. 6294 - 6299
(2008/09/21)
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- Solvent-free nucleophilic addition of N-alkylhydroxylamines to substituted nitroolefins: Formation of nitrones by a tandem process
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Nucleophilic addition of 1-methyl-2-arylethylhydroxylamine to substituted β-nitrostyrene under solvent-free conditions has led to unexpected nitrones via a tandem process involving 1,4-addition and elimination. Copyright Taylor & Francis Group, LLC.
- Amutha, Chinnadurai,Muthusubramanian, Shanmugam
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p. 328 - 337
(2008/04/01)
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- 2-Benzyl-2-methyl-2H-benzimidazole 1,3-dioxide derivatives: Spectroscopic and theoretical study
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The spectroscopic behavior of 2-benzyl-2-methyl-2H-benzimidazole 1,3-dioxide derivatives in solution was studied in terms of electronic and nuclear magnetic resonance (1H and 13C NMR) techniques. The experimental spectra were compared to the theoretical ones, obtained at DFT level, proving that the compounds adopt in solution a bird-like conformational distribution. Also, theoretically this conformational distribution resulted the most stable in gas phase. Infrared spectroscopy was used to study solid state behavior identifying experimentally the N-O stretching near to 1380, 1365 and 1225 cm-1 and the vibrational benzimidazole skeleton near to 1610 and 1590 cm-1. The vibrational spectrum was satisfactorily described by DFT calculations funding the N-O stretching as a coupled vibration near to 1470, 1350 and 1285 cm-1. The fragmentation that takes place in mass spectrometry was assigned for all of the new derivatives.
- Merlino, Alicia,Boiani, Mariana,Cerecetto, Hugo,Gonzalez, Mercedes
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p. 540 - 549
(2008/02/07)
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- Evaluation of nitroalkenes as nitric oxide donors
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Chemiluminescence experiments demonstrate that simple nitroalkenes release low levels of nitric oxide. UV and EPR measurements suggest but cannot confirm direct NO release from nitroalkenes. Given the biological activity of nitrated unsaturated fatty acids, these results suggest the possible metabolic conversion of nitroalkenes to NO.
- Gorczynski, Michael J.,Huang, Jinming,Lee, Heather,King, S. Bruce
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p. 2013 - 2017
(2008/02/05)
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