- Investigation of regioselectivity in the synthesis of spiro [pyrrolidine-2,3′-oxindoles] by use of the Huisgen reaction
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The Huisgen reaction has been used to synthesize five-membered heterocyclic compounds in high yield and with high regio and stereoselectivity. In the synthesis of spiro [pyrrolidine-2,3′-oxindole] derivatives from isatin, α-amino acids, and (E)-β-phenyl nitroolefins, two regioisomers were obtained in each reaction. The regioselectivity of the major product was found to be different from that in reported work, and was investigated at the B3LYP/6-311G*level of theory. On the basis of this new finding, several conditions, for example molar ratio, solvent, and temperature, which affect the regioselectivity of this reaction were investigated; the results obtained are discussed. It was found that the regioselectivity of this reaction was affected by solvent and temperature, irrespective of the ratio of the reactants. Low temperature and high solvent polarity leads to high regioselectivity, and protic solvents result in higher yield and regioselectivity. These results are of benefit for regioselective synthesis of some compounds.
- Chen, Gang,Miao, Yan-Qing,Zhou, Rui,Zhang, Li,Zhang, Jie,Hao, Xiao-Jiang
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Read Online
- Synthesis and catalytic activity of novel Ni-N complexes1
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A series of nickel complexes with 1,3-xylylenediamine, 1,2-diaminobenzene and 1,2-aminobenzylamine were first synthesized and characterized. The reaction of these amines with Ni(OAc)2 · 4H2O and NiCl 2 · 6H2O in methanol or tetrahydrofuran resulted in the production of four novel nickel complexes I, II, III, and IV. The structure of each complex was determined by X-ray diffraction analysis. Each complex was also characterized using elemental analysis, 1H NMR and IR. The complexes were then used to catalyze the Henry reaction, and good catalytic results (65-99%) were achieved. The catalytic activity of the complexes was determined by 1H NMR.
- Mei,Tao,Long,Ming,Liang,Rong
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Read Online
- Anti-inflammatory potential of 1-nitro-2-phenylethylene
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Inflammation is a reaction of the host to infectious or sterile stimuli and has the physiological purpose of restoring tissue homeostasis. However, uncontrolled or unresolved inflammation can lead to tissue damage, giving rise to a plethora of chronic inflammatory diseases, including metabolic syndrome and autoimmunity pathologies with eventual loss of organ function. Beta-nitrostyrene and its derivatives are known to have several biological activities, including anti-edema, vasorelaxant, antiplatelet, anti-inflammatory, and anticancer. However, few studies have been carried out regarding the anti-inflammatory effects of this class of compounds. Thereby, the aim of this study was to evaluate the anti-inflammatory activity of 1-nitro-2-phenylethene (NPe) using in vitro and in vivo assays. Firstly, the potential anti-inflammatory activity of NPe was evaluated by measuring TNF-α produced by human macrophages stimulated with lipopolysaccharide (LPS). NPe at non-toxic doses opposed the inflammatory effects induced by LPS stimulation, namely production of the inflammatory cytokine TNF-α and activation of NF-κB and ERK pathways (evaluated by phosphorylation of inhibitor of kappa B-alpha [IκB-α] and extracellular signal-regulated kinase 1/2 [ERK1/2], respectively). In a well-established model of acute pleurisy, pretreatment of LPS-challenged mice with NPe reduced neutrophil accumulation in the pleural cavity. This anti-inflammatory effect was associated with reduced activation of NF-κB and ERK1/2 pathways in NPe treated mice as compared to untreated animals. Notably, NPe was as effective as dexamethasone in both, reducing neutrophil accumulation and inhibiting ERK1/2 and IκB-α phosphorylation. Taken together, the results suggest a potential anti-inflammatory activity for NPe via inhibition of ERK1/2 and NF-κB pathways on leukocytes.
- Sugimoto, Michelle A.,Da Silva, Márcia de Jesus Amazonas,Brito, Larissa Froede,Borges, Rosivaldo dos Santos,Amaral, Flávio Almeida,Boleti, Ana Paula de Araujo,Ordo?ez, Maritza Echevarria,Tavares, Jose Carlos,Sousa, Lirlandia Pires,Lima, Emerson Silva
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- Mesoporous silica with site-isolated amine and phosphotungstic acid groups: A solid catalyst with tunable antagonistic functions for one-pot tandem reactions
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Coniuga et impera: A bifunctional solid catalyst is prepared by combining acid and base functions on mesoporous silica supports (see picture). The co-existence of these functions is shown by a two-step reaction sequence in one pot. Excellent product yields, which cannot be obtained by separated acid and base functions in one pot, show the validity of our concept. Copyright
- Shiju, N. Raveendran,Alberts, Albert H.,Khalid, Syed,Brown, David R.,Rothenberg, Gadi
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Read Online
- A noncovalent hybrid of [Pd(phen)(OAc)2] and st-DNA for the enantioselective hydroamination of β-nitrostyrene with methoxyamine
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We developed a novel Pd-catalysed enantioselective synthesis of C-N bonds using the chiral scaffold of DNA. The non-covalently linked [Pd(phen)(OAc)2] with st-DNA catalysed the Markonicov hydroamination of β-nitrostyrene with methoxyamine for the first time with >75% enantiomeric excess (ee) in an aqueous buffer (pH 7.4) at room temperature.
- Pal, Mrityunjoy,Musib, Dulal,Pal, Maynak,Rana, Gopal,Bag, Gobinda,Dutta, Subrata,Roy, Mithun
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supporting information
p. 5072 - 5076
(2021/06/21)
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- N-Heterocyclic Iod(az)olium Salts – Potent Halogen-Bond Donors in Organocatalysis
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This article describes the application of N-heterocyclic iod(az)olium salts (NHISs) as highly reactive organocatalysts. A variety of mono- and dicationic NHISs are described and utilized as potent XB-donors in halogen-bond catalysis. They were benchmarked in seven diverse test reactions in which the activation of carbon- and metal-chloride bonds as well as carbonyl and nitro groups was achieved. N-methylated dicationic NHISs rendered the highest reactivity in all investigated catalytic applications with reactivities even higher than all previously described monodentate XB-donors based on iodine(I) and (III) and the strong Lewis acid BF3.
- Boelke, Andreas,Kuczmera, Thomas J.,Lork, Enno,Nachtsheim, Boris J.
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supporting information
p. 13128 - 13134
(2021/08/09)
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- Design, Synthesis, and Biological Evaluation of Organic Nitrite (NO 2-) Donors as Potential Anticerebral Ischemia Agents
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The treatment of ischemic stroke (IS) remains a big challenge in clinics, and it is urgently needed to develop novel, safe, and effective medicines against IS. Here, we report the design, synthesis, and biological evaluation of organic NO2- donors as potential agents for the treatment of IS. The representative compound 4a was able to slowly generate low concentrations of NO2- by reaction with a thiol-containing nucleophile, and the NO2- was selectively converted into NO under ischemic/hypoxia conditions to protect primary rat neurons from oxygen-glucose deprivation and recovery (OGD/R)-induced cytotoxicity by enhancing the Nrf2 signaling and activating the NO/cGMP/PKG pathway. Treatment with 4a at 2 h before or after ischemia mitigated the ischemia/reperfusion-induced brain injury in middle cerebral artery occlusion (MCAO) rats by producing NO and enhancing Nrf2 signaling. Furthermore, 4a significantly promoted endothelial cell proliferation and angiogenesis within the ischemic penumbra. Our findings suggest that this type of NO2- donors, like 4a, may be valuable to fight IS and other ischemic diseases.
- Wu, Jianbing,Yin, Wei,Huang, Zhangjian,Zhang, Yinqiu,Jia, Jian,Cheng, Huimin,Kang, Fenghua,Huang, Kai,Sun, Tao,Tian, Jide,Xu, Xiaojun,Zhang, Yihua
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p. 10919 - 10933
(2021/08/16)
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- Electrochemical Generation of a Nonstabilized Azomethine Ylide: Access to Substituted N-Heterocycles
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Azomethine ylides are fascinating 1,3-dipoles for [3 + 2] cycloaddition reactions toward the construction ofN-heterocycles. Herein, an efficient and environmentally benign electrochemical approach for the generation of a nonstabilized azomethine ylide has been established under metal-free and external oxidant-free conditions. The resulting 1,3-dipole undergoes a [3 + 2] cycloaddition reaction with olefins. This electrosynthetic methodology indulges a straightforward and facile approach for the construction of substituted pyrrolidines.
- Kumar, Rakesh,Banerjee, Prabal
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p. 16104 - 16113
(2021/11/18)
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- Catalytic Asymmetric Construction of Tertiary Carbon Centers Featuring an α-Difluoromethyl Group with CF2H-CH2-NH2as the "building Block"
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We report here for the first time a novel difluoromethylated ketimine building block condensed by thioisatin and difluoroethylamine, offering efficient access to a broad range of enantioenriched products bearing difluoroethylamine units (27 examples, ≤98% yield, >99% ee) in the presence of quinine-derived squaramide. Further transformation of the intermediate would generate a variety of versatile functional blocks like α-difluoromethyl amines, β-amino acid, and β-diamine with retention of the enantiomeric excess at the difluoromethyl-bound carbon.
- Gao, Fengyun,Guo, Yifei,Sun, Mengmeng,Wang, Yalan,Yang, Changyan,Wang, Yuqiang,Wang, Kairong,Yan, Wenjin
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supporting information
p. 2584 - 2589
(2021/04/13)
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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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- Preparation method of beta-trans-nitroolefin
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The invention relates to a preparation method of beta-trans-nitroolefin. The method comprises: sequentially adding an olefin compound, a nitration reagent and a solvent into a reaction container, mixing the substances uniformly, and carrying out constant temperature reaction for 18h under an illumination condition to obtain a reaction solution; and sequentially carrying out drying, concentration and column chromatography treatment on the reaction solution to obtain the beta-trans-nitroolefin compound. The method is simple and practicable, low in cost and high in product yield, can realize large-scale production, and has good industrial application prospects in the aspects of functional organic material, bioactive compound and drug synthesis.
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Paragraph 0011-0017; 0024-0026; 0030-0032
(2020/06/17)
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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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- tert-Butyl Nitrite Mediated Nitro-Nitratosation of Internal Alkenes
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In an oxygen atmosphere tert-butyl nitrite (TBN) reacts with unsymmetrical internal benzylic alkenes giving nitro-nitratosation product exclusively. The γ-diaryl-substituted styrenes provided better yields compared to γ-alkyl-aryl-substituted styrenes. The higher yields for the former type of substrates is possibly dictated by the additional stability of benzylic radical due to the anchimeric assistance imparted by the γ-substituted phenyl ring. During oxidative nitration, the nitro (NO2) group adds at the non-benzylic site, whereas the nitrato group (ONO2) is attached at the relatively stable benzylic position. Under similar reaction conditions, α,β-unsaturated carboxylic acids, afforded nitroalkenes as the sole product.
- Mir, Bilal Ahmad,Rajamanickam, Suresh,Begum, Pakiza,Patel, Bhisma K.
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p. 2617 - 2625
(2020/05/08)
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- Biological evaluation and SAR analysis of novel covalent inhibitors against fructose-1,6-bisphosphatase
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Fructose-1,6-bisphosphatase (FBPase) is an attractive target for affecting the GNG pathway. In our previous study, the C128 site of FBPase has been identified as a new allosteric site, where several nitrovinyl compounds can bind to inhibit FBPase activity. Herein, a series of nitrostyrene derivatives were further synthesized, and their inhibitory activities against FBPase were investigated in vitro. Most of the prepared nitrostyrene compounds exhibit potent FBPase inhibition (IC50 3, CF3, OH, COOH, or 2-nitrovinyl were installed at the R2 (meta-) position of the benzene ring, the FBPase inhibitory activities of the resulting compounds increased 4.5–55 folds compared to those compounds with the same groups at the R1 (para-) position. In addition, the preferred substituents at the R3 position were Cl or Br, thus compound HS36 exhibited the most potent inhibitory activity (IC50 = 0.15 μM). The molecular docking and site-directed mutation suggest that C128 and N125 are essential for the binding of HS36 and FBPase, which is consistent with the C128-N125-S123 allosteric inhibition mechanism. The reaction enthalpy calculations show that the order of the reactions of compounds with thiol groups at the R3 position is Cl > H > CH3. CoMSIA analysis is consistent with our proposed binding mode. The effect of compounds HS12 and HS36 on glucose production in primary mouse hepatocytes were further evaluated, showing that the inhibition was 71% and 41% at 100 μM, respectively.
- Chen, Haifeng,Guo, Yanrong,Han, Xinya,Hu, Wei,Huang, Yunyuan,Ren, Yanliang,Tang, Zilong,Wang, Qi,Wei, Lin,Xia, Qinfei,Yan, Jufen
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supporting information
(2020/07/23)
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- Molecular Engineering of β-Substituted Oxoporphyrinogens for Hydrogen-Bond Donor Catalysis
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A new class of bifunctional hydrogen-bond donor organocatalyst using oxoporphyrinogens having increased intramolecular hydrogen-bond donor distances is reported. Oxoporphyrinogens are highly non-planar rigid macrocycles containing a multiple hydrogen bond-forming binding site. In this work, we describe the first example of non-planar OxPs as hydrogen-bond donor catalysts prepared using a molecular engineering approach of the binding site for dual activation of substrates. The introduction of β-substituents is key to the catalytic activity and the catalysts are able to catalyze 1,4-conjugate additions and sulfa-Michael additions, as well as, Henry and aza-Henry reactions at low catalyst loadings (≤ 1 mol-%) under mild conditions. Preliminary mechanistic studies have been carried out and a possible reaction mechanism has been proposed based on the bi-functional activation of both substrates through hydrogen-bonding interactions.
- Chahal, Mandeep K.,Payne, Daniel T.,Matsushita, Yoshitaka,Labuta, Jan,Ariga, Katsuhiko,Hill, Jonathan P.
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supporting information
p. 82 - 90
(2020/01/02)
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- Asymmetric synthesis of tetrahydropyran[3,2-c]quinolinones via an organocatalyzed formal [3 + 3] annulation of quinolinones and MBH 2-naphthoates of nitroolefin
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An efficient asymmetric and enantio-swithchable organocatalytic [3 + 3] annulation reaction using MBH-2-naphthoates of nitroalkenes and 4-hydroxyquinolin-2(1H)-ones has been developed. Densely substituted tetrahydropyrano[3,2-c]quinolinones scaffolds with two adjacent stereogenic centers are obtained with high yield (up to 95% yield) and good stereoselectivities (up to >20:1 dr and 96% ee) in an enantio-switchable manner. Furthermore, gram scale synthesis was achieved and the nitro group could easily transform into an amino group without any appreciable loss in the diastereo- and enantioselectivity.
- Li, Jian,Hu, Qi-Long,Chen, Xue-Ping,Hou, Ke-Qiang,Chan, Albert S.C.,Xiong, Xiao-Feng
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supporting information
p. 697 - 700
(2019/09/30)
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- A photocatalyst-free photo-induced denitroalkylation of β-nitrostyrenes with 4-alkyl substituted Hantzsch esters at room temperature
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A photocatalyst-free stereoselectively photo-induced strategy for the denitroalkylation of β-nitrostyrenes using 4-alkyl substituted Hantzsch esters as the alkyl source under xenon lamp irradiation is developed. The reaction proceeds at room temperature and affords the corresponding products in moderate to excellent yields. The oxidant di-t-butyl peroxide serves as an efficient radical initiator under irradiation of a Xenon lamp, initiating alkyl radicals from the 4-alkyl substituted Hantzsch esters.
- Duan, Chunying,Hao, Xinyu,Jin, Kun,Li, Yaming,Wang, Jiaao,Zhang, Rong,Zhang, Siyu
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supporting information
(2020/02/18)
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- NCC Pincer Ni (II) Complexes Catalyzed Hydrophosphination of Nitroalkenes with Diphenylphosphine
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An efficient NCC pincer Ni (II)-catalyzed hydrophosphination of nitroalkenes with diphenylphosphine has been developed. Under the optimized conditions, both (hetero)aromatic and aliphatic nitroalkenes were well tolerated, irrespective of electronic effect, to provide the corresponding products in up to 99% yield.
- Yan, Jing,Wang, Yan-Bing,Hou, Senyao,Shi, Linlin,Zhu, Xinju,Hao, Xin-Qi,Song, Mao-Ping
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- Synthetic Diversity from a Versatile and Radical Nitrating Reagent
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We leverage the slow liberation of nitrogen dioxide from a newly discovered, inexpensive succinimide-derived reagent to allow for the C?H diversification of alkenes and alkynes. Beyond furnishing a library of aryl β-nitroalkenes, this reagent provides unparalleled access to β-nitrohydrins and β-nitroethers. Detailed mechanistic studies strongly suggest that a mesolytic N?N bond fragmentation liberates a nitryl radical. Using in situ photo-sensitized, electron paramagnetic resonance spectroscopy, we observed direct evidence of a nitryl radical in solution by nitrone spin-trapping. To further exhibit versatility of N-nitrosuccinimide under photoredox conditions, the late-stage diversification of an extensive number of C?H partners to prepare isoxazolines and isoxazoles is presented. This approach allows for the formation of an in situ nitrile oxide from a ketone partner, the presence of which is detected by the formation of the corresponding furoxan when conducted in the absence of a dipolarophile. This 1,3-dipolar cycloaddition with nitrile oxides and alkenes or alkynes proceeds in a single-operational step using a mild, regioselective, and general protocol with broad chemoselectivity.
- Zhang, Kun,Jelier, Benson,Passera, Alessandro,Jeschke, Gunnar,Katayev, Dmitry
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supporting information
p. 12929 - 12939
(2019/09/17)
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- Preparation method of nitroolefin derivative with nitrate as nitro source
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The invention relates to a nitroolefin derivative with nitrate as nitro source and a preparation method thereof. Under the atmosphere of nitrogen, an olefin compound, nitrate, trimethylchlorosilane (TMSC1) and copper salt are stirred in acetonitrile at 0-30 DEG C; in addition, the reaction degree is monitored by using a TLC point plate; after the olefin compound is completely consumed, alkali is added to an obtained mixture to be stirred for 20-30 min; then after a solvent is removed from an obtained mixture by using a rotary evaporator, the nitroolefin derivative can be obtained through silicagel column purification. Compared with the prior art, the nitroolefin derivative with the nitrate as the nitro source, provided by the invention, has the advantages of mild reaction condition, high yield, high E type selectivity and the like.
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Paragraph 0042-0048
(2019/08/20)
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- Metal-free, room temperature, acid-K2S2O8 mediated method for the nitration of olefins: An easy approach for the synthesis of nitroolefins
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Here, we have developed a simple, room temperature method for the nitration of olefins by using inexpensive sodium nitrite as a source of nitro groups in the presence of trifluoroacetic acid (TFA) and potassium persulfate (K2S2O8) under an open atmosphere. Styrenes and mono-substituted olefins give stereo-selective corresponding E-nitroolefins under optimized conditions, however, 1,1-bisubstituted olefins give a mixture of E- and Z-nitroolefins. The optimized conditions work well with electron-donating, electron-withdrawing, un-substituted and heterocyclic styrenes and mono-substituted olefins and give corresponding nitroolefins with good to excellent yields.
- Ambala, Srinivas,Singh, Rohit,Singh, Maninder,Cham, Pankaj Singh,Gupta, Ria,Munagala, Gurunadham,Yempalla, Kushalava Reddy,Vishwakarma, Ram A.,Singh, Parvinder Pal
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p. 30428 - 30431
(2019/10/04)
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- Nitration-Peroxidation of Alkenes: A Selective Approach to β-Peroxyl Nitroalkanes
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Nitration-peroxidation of alkenes for the synthesis of β-peroxyl nitroalkanes has been developed by using tert-butyl nitrite and tert-butyl hydroperoxide. The method presents a new and selective difunctionalization of alkenes to introduce a nitro group and a peroxyl group across the double bonds of alkenes under mild conditions. A radical reaction pathway is proposed by experimental and theoretical studies.
- Chen, Yuanjin,Ma, Yangyang,Li, Liangkui,Jiang, Hao,Li, Zhiping
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supporting information
p. 1480 - 1483
(2019/02/26)
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- Poly(ethylene glycol) supported metal nitrates as well-organized reagents for hunsdiecker conversion of α,β-unsaturated acids to β-nitrostyrenes under solvent and acid-free conditions
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Poly(ethylene glycol) (PEG) supported metal nitrates such as ferric nitrate and manganese nitrate were accomplished as well-organized reagents for Hunsdiecker conversion of α,β-unsaturated acids to β-nitrostyrenes under acid-free and solvent free conditions using grindstone technique. However, in the case of unsaturated aliphatic acids, nitro alkene derivatives were obtained as products. PEG-400 was found the best among the other PEGs (PEG-200,300, 400, 600, 3000 and 6000) used in this protocol.
- Ramesh,Shylaja,Ramgopal,Rao, A. Sambashiva,Rajanna
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p. 1798 - 1800
(2019/07/17)
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- Discovery of novel allosteric site and covalent inhibitors of FBPase with potent hypoglycemic effects
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Fructose-1,6-bisphosphatase (FBPase) is an essential enzyme of GNG pathway. Significant advances demonstrate the FBPase plays a critical role in treatment of diabetes. Numerous FBPase inhibitors were developed by targeting AMP site, nevertheless, none of these inhibitors has exhibited suitable potency and druggability. Herein, a new allosteric site (C128) on FBPase was discovered, and several nitrostyrene compounds exhibiting potent FBPase inhibitions were found covalently bind to C128 site on FBPase. Mutagenesis suggest that C128 is the only cysteine that can influence FBPase inhibition, the N125–S124–S123 pathway was most likely involved in allosteric signaling transmission between C128 and active site. However, these nitrostyrenes may bind with multiple cysteine besides C128 in FBPase. To improve pocket selectivity, a series of novel compounds (14a-14n) were re-designed rationally by integrating fragment-based covalent virtual screening and machine-learning-based synthetic complexity evaluation. As expected, the mass spectrometry validated that the proportion of title compounds binding to the C128 in FBPase was significantly higher than that of nitrostyrenes. Notably, under physiological and pathological conditions, the treatment of compounds 14b, 14c, 14i or 14n led to potent inhibition of glucose production, as well as decreased triglyceride and total cholesterol levels in mouse primary hepatocytes. We highlight a novel paradigm that molecular targeting C128 site on FBPase can have potent hypoglycemic effect.
- Huang, Yunyuan,Wei, Lin,Han, Xinya,Chen, Haifeng,Ren, Yanliang,Xu, Yanhong,Song, Rongrong,Rao, Li,Su, Chen,Peng, Chao,Feng, Lingling,Wan, Jian
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supporting information
(2019/10/08)
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- Facile Synthesis of 1,3,5-Triarylbenzenes and 4-Aryl-NH-1,2,3-Triazoles Using Mesoporous Pd-MCM-41 as Reusable Catalyst
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We report mesoporous nano-Pd-MCM-41 catalyzed rapid and efficient synthesis of 1,3,5-triarylbenzenes via de-nitrative cyclotrimerization of β-nitrostyrenes. All the reactions were very fast and high yielding. The Pd-MCM-41 was also very effective in catalyzing de-nitrative [3+2] cycloaddition of β-nitrostyrenes with TMSN3 to synthesize 4-aryl-NH-1,2,3-triazoles. The catalyst was reused at least up to eight times with minimum loss of catalytic activity.
- Saha, Arijit,Wu, Chia-Ming,Peng, Rui,Koodali, Ranjit,Banerjee, Subhash
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p. 104 - 111
(2019/01/04)
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- A chiral bicyclic skeleton-tethered bipyridine-Zn(OTf)2 complex as a Lewis acid: Enantioselective Friedel-Crafts alkylation of indoles with nitroalkenes
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A conformationally rigid chiral bicyclic skeleton tethered bipyridine-Zn(OTf)2 complex facilitated the enantioselective Friedel-Crafts alkylation of indoles with trans-β-nitroarylalkenes in an enantioselective manner at elevated temperature. Indoles reacted smoothly with β-nitroarylalkenes to generate the corresponding 3-(2-nitroalkyl)indoles in good to excellent yields (up to 94%) with moderate to excellent enantioselectivities (up to 91%). The stereochemical outcome of the product from indole and trans-β-nitrostyrene in the presence of the CRCB tethered bipyridine-Zn(OTf)2 complex and the DFT calculation of the CRCB tethered bipyridine-Zn:trans-β-nitrostyrene complex support the si-face attack of indole on trans-β-nitrostyrene.
- Venkatanna, Kesa,Yeswanth Kumar, Santhakumar,Karthick, Muthupandi,Padmanaban, Ramanathan,Ramaraj Ramanathan, Chinnasamy
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p. 4077 - 4086
(2019/04/30)
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- Substituted Pyrrolidine Amides II
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The invention relates to compounds according to general formula (I), which act as modulators of the glucocorticoid receptor and can be used in the treatment and/or prophylaxis of disorders which are at least partially mediated by the glucocorticoid receptor.
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Paragraph 0452-0454
(2019/07/03)
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- 3,4-dihydrogen-benzo[f][1,4] thiazepine*-5(2H)-ketones and their applications in medicine
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The invention belongs to the technical field of medicine and relates to 3,4-dihydrogen-benzo[f][1,4] thiazepine*-5(2H)-ketones with the general structure of formula I and their applications in medicine. These compounds selectively inhibit the activity of glycogen synthesis kinases-3 beta (GSK 3beta), which can be used to prepare medicaments for preventing and/or treating diseases having GSK 3betaabnormal pathological characteristics, such as cancer, neurological diseases, inflammation, metabolic syndrome, and the like.
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Paragraph 0027; 0029; 0030; 0031
(2019/11/20)
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- Iodine monobromide catalysed regioselective synthesis of 3-arylquinolines from α-aminoacetophenones and: Trans -β-nitrostyrenes
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A simple and efficient method for regioselective synthesis of 3-arylquinolines is described from α-aminoacetophenones and trans-β-nitrostyrenes using 20 mol% iodine monobromide as a catalyst in acetonitrile solvent at 80 °C. The present method involves tandem reaction of α-aminoacetophenones and trans-β-nitrostyrenes, formation of two new C-C bonds and cleavage of one C-C bond in a single step. The salient features of the protocol are metal- and oxidant-free reaction conditions, broad substrate scope, and good yields.
- Gattu, Radhakrishna,Mondal, Santa,Ali, Saghir,Khan, Abu T.
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supporting information
p. 347 - 353
(2019/01/10)
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- Concerted catalysis by nanocellulose and proline in organocatalytic Michael additions
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Cellulose nanofibers (CNFs) have recently attracted much attention as catalysts in various reactions. Organocatalysts have emerged as sustainable alternatives to metal-based catalysts in green organic synthesis, with concerted systems containing CNFs that are expected to provide next-generation catalysis. Herein, for the first time, we report that a representative organocatalyst comprising an unexpected combination of 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO)-oxidized CNFs and proline shows significantly enhanced catalytic activity in an asymmetric Michael addition.
- Ranaivoarimanana, Naliharifetra Jessica,Kanomata, Kyohei,Kitaoka, Takuya
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supporting information
(2019/04/05)
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- Triarylimidazo[1,2-a]pyridine-8-carbonitriles: solvent-free synthesis and their anti-cancer evaluation
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In this study, we have presented the synthesis of novel 2,5,7-triarylimidazo[1,2-a]pyridine-8-carbonitriles from 2-amino-4,6-diarlypyridine-3-carbonitrile and nitrostyrene using FeCl3 (20 mol%) as Lewis acid under solvent-free conditions. A library of compounds with diverse substitutions have also been synthesized and screened for in-vitro anti-cancer activity against various cell lines such as A549 (Lung), HCT-116 (Colon), SW-620 (Colon), and MIAPACA (Pancreas).
- Gupta, Annah,Sasan, Sonakshi,Kour, Avneet,Nelofar, Nargis,Manikrao Mondhe, Dilip,Kapoor, Kamal K.
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supporting information
p. 1813 - 1822
(2019/05/15)
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- Catalytic and Mechanistic Developments of the Nickel(II) Pincer Complex-Catalyzed Hydroarsination Reaction
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Synthetic challenges have significantly slowed the development of the catalytic asymmetric hydroarsination reaction despite it being a highly attractive C?As bond formation methodology. In addition, there is a poor understanding of the main reaction steps in such reactions which limit further development in the field. Herein, key intermediates of the hydroarsination reaction catalyzed by a PCP NiII-Cl pincer complex are presented upon investigating the reaction with DFT calculations, conductivity measurements, NMR spectroscopy, and catalytic screening. The novel Ni–Cl–As interaction proposed was then contrasted against known NiII-catalyzed hydrophosphination reactions to highlight dissimilarities between them even though P and As share a close group relationship. Lastly, the asymmetric hydroarsination of nitroolefins was further developed to furnish a library of chiral organoarsines in up to 99 % yield and 80 % ee under mild conditions (?20 °C to RT) between 5 to 210 mins.
- Tay, Wee Shan,Lu, Yunpeng,Yang, Xiang-Yuan,Li, Yongxin,Pullarkat, Sumod A.,Leung, Pak-Hing
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supporting information
p. 11308 - 11317
(2019/08/07)
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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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- Synthesis of nitroolefins and nitroarenes under mild conditions
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1,3-Disulfonic acid imidazolium nitrate {[Dsim]NO3} was prepared and characterized as a new ionic liquid and nitrating agent for the ipso-nitration of various arylboronic acids and nitro-Hunsdiecker reaction of different α,β-unsaturated acids and benzoic acid derivatives, by in situ generation of NO2 to give various nitroarenes and nitroolefins without using any cocatalysts and solvents under mild conditions.
- Zarei, Mahmoud,Noroozizadeh, Ehsan,Moosavi-Zare, Ahmad R.,Zolfigol, Mohammad A.
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p. 3645 - 3650
(2018/04/14)
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- tert-Butyl Nitrite Mediated Different Functionalizations of Internal Alkenes: Paths to Furoxans and Nitroalkenes
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tert-Butyl nitrite (TBN) reacts differently with various internal alkenes leading to interesting and useful products. Synthesis of 1,2,5-oxadiazole-N-oxides (furoxans) has been achieved from internal alkenes using tert-butyl nitrite (TBN), quinoline and K2S2O8. Under an identical reaction condition α,β-unsaturated carboxylic acids and cyclic and acyclic internal alkenes both afforded nitroalkenes as the sole product via decarboxylative and direct nitration path respectively. (Figure presented.).
- Mir, Bilal Ahmad,Singh, Sarangthem Joychandra,Kumar, Ritush,Patel, Bhisma K.
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p. 3801 - 3809
(2018/09/18)
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- Discovery of Cytochrome P450 4F11 Activated Inhibitors of Stearoyl Coenzyme A Desaturase
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Stearoyl-CoA desaturase (SCD) catalyzes the first step in the conversion of saturated fatty acids to unsaturated fatty acids. Unsaturated fatty acids are required for membrane integrity and for cell proliferation. For these reasons, inhibitors of SCD represent potential treatments for cancer. However, systemically active SCD inhibitors result in skin toxicity, which presents an obstacle to their development. We recently described a series of oxalic acid diamides that are converted into active SCD inhibitors within a subset of cancers by CYP4F11-mediated metabolism. Herein, we describe the optimization of the oxalic acid diamides and related N-acyl ureas and an analysis of the structure-activity relationships related to metabolic activation and SCD inhibition.
- Winterton, Sarah E.,Capota, Emanuela,Wang, Xiaoyu,Chen, Hong,Mallipeddi, Prema L.,Williams, Noelle S.,Posner, Bruce A.,Nijhawan, Deepak,Ready, Joseph M.
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p. 5199 - 5221
(2018/06/13)
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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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- Synthetic method of (E)-alkenyl sulfone compounds
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The invention discloses a synthetic method of (E)-alkenyl sulfone compounds. The method comprises the following steps: beta-nitroolefin compounds shown as formula I in the description, sulfohydrazidecompounds shown as formula II in the description, an iodine-containing nonmetal catalyst and a peroxide oxidizing agent are mixed for a reaction, and a mixture obtained after the reaction is subjectedto postprocessing, and the (E)-alkenyl sulfone compounds shown as formula III in the description are obtained. Beta-nitroolefin compounds, the sulfohydrazide compounds, the iodine-containing nonmetalcatalyst and the peroxide oxidizing agent are taken as main raw materials, the corresponding (E)-alkenyl sulfone compounds are synthesized through free radical reaction, the iodine-containing nonmetal catalyst iodine or tetrabutylammonium iodide is used, the raw materials are simple, easily available, cheap, non-toxic and pollution-free to the environment, the dosage of the catalyst is small, thecatalyst has higher specificity for the reaction, synthetic reaction time can be shortened, the problem that the metal catalyst is difficult to separate in the prior art can be well solved, postprocessing difficulty is reduced, yield of the final product is increased, and purity of the final product is improved.
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Paragraph 0040; 0042
(2019/01/14)
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- Enantioselective Conjugate Addition of 2-Acylimidazoles with Nitroalkenes Promoted by Chiral-at-Metal Rhodium(III) Complexes
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An enantioselective conjugate addition of 2-acylimidazoles with nitroalkenes catalyzed by chiral-at-metal rhodium(III) complex under mild reaction conditions was developed, affording versatile γ-nitro ketone skeletons in good yields with excellent enantioselectivities (up to >99% ee). (Figure presented.).
- Thota, Ganesh Kumar,Sun, Gui-Jun,Deng, Tao,Li, Yi,Kang, Qiang
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supporting information
p. 1094 - 1098
(2018/01/22)
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- Direct dihalo-alkoxylation of nitroalkenes leading to β,β-dihalo-β-nitroethyl alkyl ethers
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A highly efficient one-pot synthesis of β,β-dihalo-β-nitroethyl alkyl ethers is achieved by the treatment of nitroalkenes with alcohols and N-halosuccinimides in the presence of sodium hydride. The notable advantages of this protocol are that it involves simple experimental manipulations and tolerates a wide range of functional groups. Further transformations of the obtained ethers, such as allylation and conversion to β,β-dihalogenated vinyl ethers, are also investigated.
- Hao, Feiyue,Yokoyama, Soichi,Nishiwaki, Nagatoshi
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p. 2768 - 2775
(2018/04/26)
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- One-Step, Effective, and Cascade Syntheses of Highly Functionalized Cyclopentenes with High Diastereoselectivity
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Tetrabutylammonium fluoride works as an effective organocatalyst for the cycloaddition between phenacylmalononitriles and electron-deficient olefins (having substituent groups of NO2, CHO, and COR), providing a facile synthetic route to versatile multifunctionalized cyclopentenes having an allylic quaternary carbon center bearing both cyano and carboxamide groups with high yields and high diastereoselectivity. Preliminary studies reveal that these functionalized cyclopentenes are convenient precursors for making α-cyano-functionalized cyclopentadienone oximes.
- Alishetty, Suman,Shih, Hong-Pin,Han, Chien-Chung
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p. 2513 - 2516
(2018/05/17)
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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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- Sulfonation of carbonized xylan-type hemicellulose: A renewable and effective biomass-based biocatalyst for the synthesis of O- and N-heterocycles
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The application of biomass-based carbonaceous solid acids in catalysis is attracting increasing attention in the field of chemistry. In this study, a heterogeneous carbon-based solid acid biocatalyst (CXH-SO3H) with regular spherical structure was synthesized from xylan-type hemicellulose (XH) by a simple two-step method. The catalyst was successfully applied in the synthesis of O- and N-heterocycles with yields of 80-99% and 60-97%, respectively. In view of environment and economy, CXH-SO3H shows the merits of environmental friendliness, easy operation, simple work-up, excellent yields, and the avoidance of use of organic solvents and expensive catalysts. Moreover, the as-synthesized solid acid catalyst could be used for several cycles without significant loss in its catalytic activity. The results of FT-IR, XRD, and SEM showed that no distinct differences in physico-chemical structures of CXH-SO3H were observed. Thus, the eco-friendly CXH-SO3H catalyst is a promising candidate for green synthesis of O- and N-heterocycles from low-cost feed-stocks and has good prospect in partially substituting commercially available solid and liquid acid catalysts and precious metal catalysts.
- Ma, Jiliang,Peng, Xinwen,Zhong, Linxin,Sun, Runcang
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supporting information
p. 9140 - 9150
(2018/06/11)
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- Intermolecular [2+2] Photocycloaddition of β-Nitrostyrenes to Olefins upon Irradiation with Visible Light
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The title compounds were found to undergo a [2+2] photocycloaddition with olefins at λ = 419 nm in CH 2 Cl 2 as the solvent. The resulting cyclobutanes were isolated in yields of 32-87% (11 examples) and showed a defined relative configuration at C1/C4 in the major diastereoisomer (nitro and aryl trans). The analysis of side products and triplet sensitization experiments support a mechanistic scenario in which a 1,4-diradical is formed as a key intermediate.
- Mohr, Lisa-Marie,Bach, Thorsten
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p. 2946 - 2950
(2017/12/14)
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- Method for catalytically synthesizing (E)-beta-nitrostyrene derivatives based on tetraarylporphyrin iron
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The invention discloses a method for catalytically synthesizing (E)-beta-nitrostyrene derivatives based on tetraarylporphyrin iron. According to the method, styrene derivatives are subjected to one-pot reaction in a system containing tetraarylporphyrin iron (III), ammonium iodide and tert-butyl hydroperoxide to generate the (E)-beta-nitrostyrene derivatives. The method is capable of synthesizing beta-nitrostyrene derivatives with high E stereoselectivity with high yield under the mild reaction condition.
- -
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Paragraph 0047-0050
(2017/08/31)
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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 0055-0061; 0152; 0159; 0166; 0180
(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; 0059; 0060; 0061; 0062; 0152-0187
(2017/09/05)
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- Synthesis method of (E)-beta-nitrostyrene
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The invention discloses a synthesis method of (E)-beta-nitrostyrene. In the method, the (E)-beta-nitrostyrene is produced through a one-pot reaction to styrene in a system comprising tetraaryl ferric porphyrin (III), ammonium halide salt and tert-butyl hydroperoxide. The method can synthesize the (E)-beta-nitrostyrene, which has high E-stereoscopic selectivity, under gentle reaction conditions at high yield.
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Paragraph 0037-0085
(2017/09/26)
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- High-selectivity (E)-beta-nitrostyrene derivative one-pot synthesizing method
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The invention discloses a high-selectivity (E)-beta-nitrostyrene derivative one-pot synthesizing method. In air or sealed environment, styrene derivative generates one-pot reaction in a system containing tetra-acryl ferroporphyrin (III), ammonium iodide and tert-butyl hydroperoxide to generate (E)-beta-nitrostyrene derivative. The method achieves the purpose of synthesizing the beta-nitrostyrene derivative with high E three-dimensional selectivity in high yield under moderate reaction conditions.
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Paragraph 0044-0051; 0099; 0106; 0120; 0127
(2018/03/28)
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- Stereoselective Synthesis of Alkenyl Silanes, Sulfones, Phosphine Oxides, and Nitroolefins by Radical C-S Bond Cleavage of Arylalkenyl Sulfides
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A radical-mediated approach has been introduced for the C-S bond activation of arylalkenyl sulfides. The protocol provides an efficient approach for the generation of various alkenes including alkenyl silanes, sulfones, phosphine oxides, and nitroolefins. In most cases, these radical substitutions are performed under metal-free conditions with stereospecificity.
- Lin, Ya-mei,Lu, Guo-ping,Wang, Rong-kang,Yi, Wen-bin
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supporting information
p. 1100 - 1103
(2017/03/15)
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- Fe(III)/Pyridine-Mediated Decarboxylative Nitration of α,β-Unsaturated Acids with Iron Nitrate
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A novel and efficient method for the synthesis of (E)-nitroolefins in moderate to excellent yields is developed by Fe(III)/pyridine-mediated decarboxylative nitration of α,β-unsaturated acids with iron nitrate. A series of α,β-unsaturated acids are well tolerated in this procedure.
- Yang, Zan,Li, Jiao,Hua, Jie,Yang, Tao,Yi, Jianmin,Zhou, Congshan
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p. 1079 - 1082
(2017/05/19)
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- Chloro/bromotrimethylsilane-Cu(NO3)2·3H2O: Safe and efficient reagent system for the decarboxylative ipso-nitration and dibromination of cinnamic acids
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Further synthetic potential of halotrimethylsilane-nitrate salt mixture is revealed. A mixture of TMSX-Cu(NO3)2·3H2O system is found to be an efficient reagent system for both the decarboxylative nitration (ipso-nitration) when X?=?Cl, and dibromination of cinnamic acids, with X?=?Br, under mild conditions. The reactions are safe and simple, affording the corresponding products (E)-β-nitrostyrenes, and anti-2,3-dibromo-3-phenylpropanoic acids in high yields with high selectivity in a relatively short time. Use of hazardous and toxic nitrating systems such as acetyl nitrate and brominating agents such as molecular bromine can be avoided.
- Roshandel, Sahar,Gurung, Laxman,Mathew, Thomas,Prakash, G.K. Surya
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supporting information
p. 2842 - 2845
(2017/06/27)
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- Selective One-Pot Two-Step C?C Bond Formation using Metal–Organic Frameworks with Mild Basicity as Heterogeneous Catalysts
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Copper-ion-exchanged nickel pyrazolate frameworks behave as selective heterogeneous catalysts for the one-pot, two-step (Henry reaction/Michael type addition) synthesis of neuroactive pharmaceutical intermediates starting from nitromethane and benzaldehyde. Tuning the basicity of multifunctional metal–organic framework catalysts through ion exchange with copper(II) cations allows the tandem C?C bond-forming process to be selectively directed towards the desired pharmaceutical intermediate.
- Cirujano, Francisco G.,López-Maya, Elena,Rodríguez-Albelo, Marleny,Barea, Elisa,Navarro, Jorge A. R.,De Vos, Dirk E.
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p. 4019 - 4023
(2017/11/15)
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