- Regioselective Opening of Nitroepoxides with Unsymmetrical Diamines
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Nitroepoxides are easily transformed into benzodiazepines, tetrahydrobenzodiazepines, imidazopyridines, and N-alkyl tetrahydroquinoxalines by treatment with 2-aminobenzylamines, 2-aminopyridines, and N-alkyl 1,2-diaminobenzenes, respectively. Regioselectivity is controlled through attack of the most nucleophilic nitrogen of the unsymmetrical diamine to the β position of the epoxide. These reactions represent an efficient way to prepare privileged bioactive structures.
- Nosood, Yazdanbakhsh L.,Ziyaei Halimehjani, Azim,González, Florenci V.
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p. 1252 - 1258
(2018/02/09)
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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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- 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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- Catalytic enantioselective epoxidation of nitroalkenes
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Nitroepoxides are potentially exploitable as synthons with vicinal electrophilic centers. Nevertheless, although advances have been made in the field, enantioselective epoxidation of nitroalkenes is still a challenging process. Herein we show a convenient procedure for the preparation of optically active nitroepoxides in high enantiomeric excess and high chemical yield. The kinetic data of the best catalyst have been examined using computational methods based on DFT calculations. Interestingly, the results demonstrate that the enantioselectivity of the epoxidation of nitroalkenes by this kind of catalyst is not only kinetically but also thermodynamically controlled.
- Vidal-Albalat,?widerek,Izquierdo,Rodríguez,Moliner,González
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supporting information
p. 10060 - 10063
(2016/08/15)
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- FLUOROMETHYL-SUBSTITUTED PYRROLE CARBOXAMIDES III
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The invention relates to pyrrole carboxamides bearing a fluoromethyl- moiety as voltage gated calcium channel blockers, to pharmaceutical compositions containing these compounds and also to these compounds for use in the treatment and/or prophylaxis of pa
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Page/Page column 56
(2015/07/07)
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- FLUOROMETHYL-SUBSTITUTED PYRROLE CARBOXAMIDES IV
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The invention relates to pyrrole carboxamides bearing a fluoromethyl- moiety as voltage gated calcium channel blockers, to pharmaceutical compositions containing these compounds and also to these compounds for use in the treatment and/or prophylaxis of pain and further diseases and/or disorders.
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Page/Page column 49
(2015/07/07)
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- FLUOROMETHYL-SUBSTITUTED PYRROLE CARBOXAMIDES
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The invention relates to pyrrole carboxamides bearing a fluoromethyl-moiety as voltage gated calcium channel blockers, to pharmaceutical compositions containing these compounds and also to these compounds for use in the treatment and/or prophylaxis of pain and further diseases and/or disorders.
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Paragraph 0669; 0670
(2014/03/25)
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- FLUOROMETHYL-SUBSTITUTED PYRROLE CARBOXAMIDES
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The invention relates to pyrrole carboxamides bearing a fluoromethyl- moiety as voltage gated calcium channel blockers, to pharmaceutical compositions containing these compounds and also to these compounds for use in the treatment and/or prophylaxis of pain and further diseases and/or disorders.
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Page/Page column 96
(2014/03/25)
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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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- 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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- 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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- 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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- A convenient procedure for the synthesis of 3-substituted 5,6-dihydro-4H-1,2-oxazines from nitroethane
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A novel and efficient four-step procedure for the synthesis of C-3-functionalised 5,6-dihydro-4H-1,2-oxazines from nitroethane is described. It includes preparation of 3-methyl-substituted six-membered cyclic nitronates, 3-(bromomethyl)-substituted 5,6-dihydro-4H-1,2-oxazines as intermediates, and nucleophilic substitution of bromine. Total yields of the target C-3-functionalised oxazines are 15-30% from nitroethane. Georg Thieme Verlag Stuttgart.
- Sukhorukov, Alexey Yu.,Klenov, Michael S.,Ivashkin, Pavel E.,Lesiv, Alexey V.,Khomutova, Yulya A.,Ioffe, Sema L.
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- Borrowing hydrogen: Iridium-catalysed reactions for the formation of C-C bonds from alcohols
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Alcohols have been employed as substrates for C-C bond-forming reactions which involve initial activation by the temporary removal of hydrogen to form an aldehyde. The intermediate aldehyde is converted into an alkene via a Horner-Wadsworth-Emmons reaction, nitroaldol and aldol reactions. The 'borrowed hydrogen' is then returned to the alkene to form a C-C bond. The Royal Society of Chemistry 2006.
- Black, Phillip. J.,Cami-Kobeci, Gerta,Edwards, Michael G.,Slatford, Paul A.,Whittlesey, Michael K.,Williams, Jonathan M. J.
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p. 116 - 125
(2007/10/03)
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- Supported organic catalysts: Synthesis of (E)-nitrostyrenes from nitroalkanes and aromatic aldehydes over propylamine supported on MCM-41 silica as a reusable catalyst
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MCM-41-supported propylamine showed high catalytic efficiency in the nitroaldol condensation between nitroalkanes and aromatic aldehydes.
- Demicheli, Giuseppina,Maggi, Raimondo,Mazzacani, Alessandro,Righi, Paolo,Sartori, Giovanni,Bigi, Franca
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p. 2401 - 2403
(2007/10/03)
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- Asymmetric reduction of nitroalkenes with baker's yeast
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Various α,β-disubstituted and trisubstituted nitroalkenes were chemoselectively reduced with baker's yeast to the corresponding nitroalkanes. Stereoselectivities of the reduction of α,β-disubstituted nitroalkenes were modest to low, and e.e.s up to 52% were obtained. Trisubstituted nitroalkenes could be reduced to the corresponding nitroalkanes with excellent enantioselectivities, moderate diastereoselectivities and in good yield.
- Kawai, Yasushi,Inaba, Yoshikazu,Tokitoh, Norihiro
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p. 309 - 318
(2007/10/03)
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- Zeolite as base catalyst: Nitroaldolic condensation
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The use of heterogeneous catalysts in producing petrochemicals and fine chemicals is one of the most successful lines in catalysis research. They may replace dangerous, corrosive, or toxic catalysts in some cases. The use of zeolites as main catalysts in petrochemical cracking reactions and in oil processing is a case of specific importance. The activity and selectivity of alkaline Y and X zeolites in promoting the nitroaldolic condensation of aromatic aldehydes with nitroalkanes affording nitroalkenes were studied. The reaction was promoted by the intrinsic basicity of the zeolites that increased with increases in both the aluminum content in the framework and the radius of the counter cation. The zeolite cages were microreactors, the walls of which were the basic sites whose number and strength could be controlled by choosing the chemical composition. The activity of substituted benzaldehyde revealed the influence of electronic effects. Steric factors played a critical role regarding the nitroalkanes; the combined effect of shape selectivity and basicity had to be considered in the heterogeneous nitroaldolic condensation.
- Ballini, Roberto,Bigi, Franca,Gogni, Elena,Maggi, Raimondo,Sartori, Giovanni
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p. 348 - 353
(2007/10/03)
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- An improved synthesis of conjugated nitroolefins
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β-Nitro alcohols 1 react with triphenylphosphine/carbon tetrachloride/triethylamine under reflux to give the corresponding nitroolefins 2 in good yields (80-95%). Other groups such as tertiary hydroxyl, ether, halide etc. remain unaffected, and the nitroolefins so produced are exclusively the (E)-isomers.
- Saikia,Barua,Sharma,Ghosh
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p. 685 - 686
(2007/10/02)
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- HENRY CONDENSATION UNDER HIGH PRESSURE. 2. EFFECT OF AROMATIC ALDEHYDE TYPE AND PRESSURE ON THE YIELD OF ω-NITROSTYRENES AND SECONDARY PROCESSES
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Condensation of aromatic aldehydes (I)-(XX) with EtNO2 and n-PrNO2 in AcOH in the presence of AcONH4 or i-BuNH2 gives primarily ω-nitrostyrenes (Ia, b) - (XXa, b) and small quantities of nitriles (Ic) - (XXc), oximes (Id) - (XXd), and ketones (Ie, f) - (XXe, f).The yields of (Ia, b) - (XXa, b) at P = 1 atm are higher for acceptor substitutents on the aromatic ring whereas at P = 10 kbar, they are higher for donor substituents.High pressures suppress the formation of (Ic-f) - (XXc-f) and the Z-isomers of (Ia, b) - (XXa, b).The high pressure technique is especially useful in the preparation of donor-substituted (Ia, b) - (XXa, b) which are intermediates in the synthesis of the psychotropic β-phenylethylamines.
- Agafonov, N. E.,Sedishev, I. P.,Dudin, A. V.,Kutin, A. A.,Stashina, G. A.,Zhulin, V. M.
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p. 366 - 372
(2007/10/02)
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- Reaction of β-nitrostyrenes with benzene catalyzed by trifluoromethanesulfonic acid. Formation and reaction of n,n-dihydroxyiminium-benzyl dications
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β-Nitrostyrenes are diprotonated on the nitro group to yield N,N-dihydroxyiminium-benzyl dications in trifluoromethanesulfonic acid. These dications comprise a new class of reagents that can react with benzene. The reaction is dependent on the substituent (H or alkyl group) at the β-position of nitrostyrene: β-nitrostyrene yields diphenylacetophenoneoxime, and β-methyl-β-nitrostyrene yields acetophenoneoxime and triphenylmethane. An essentially common mechanism is suggested to be involved in both reactions. These reactions are novel examples of acidcatalyzed reactions of nitro olefins.
- Ohwada, Tomohiko,Ohta, Toshiharu,Shudo, Koichi
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p. 297 - 305
(2007/10/02)
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