- Palladium-catalyzed reaction of aryl iodides with ortho-bromoanilines and norbornene/norbornadiene: Unexpected formation of dibenzoazepine derivatives
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Expecting the unexpected: The title reaction leads to satisfactory yields of dihydrodibenzoazepines 1-a from norbornene. The dibenzoazepines 2 can also be accessed from compounds of type 1-b when norbornadiene is used as a reactant. Theoretical studies show that the reaction represents a chelation-driven deviation from the usual selectivity observed in the presence of ortho-substituents on the aryl iodide.
- Della Ca', Nicola,Maestri, Giovanni,Malacria, Max,Derat, Etienne,Catellani, Marta
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- Highly selective hydrogenation of halogenated nitroarenes over Ru/CN nanocomposites by: In situ pyrolysis
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A highly chemoselective and recyclable ruthenium catalyst for the hydrogenation of halogenated nitroarenes has been prepared via the simple in situ calcination of a mixture of melamine, glucose and ruthenium trichloride. Superfine Ru particles (2.3 ± 0.3 nm) were obtained and highly dispersed in the nitrogen-doped carbon matrix. The Ru/CN catalyst smoothly transforms a variety of halogenated nitroarenes to the corresponding haloanilines with high intrinsic activity (e.g. TOF = 1333 h-1 for p-chloronitrobenzene) and selectivity of more than 99.6percent. Furthermore, through an analysis of the products in the reaction process, it was concluded that there are two parallel reaction pathways (a direct pathway and an indirect pathway) for the hydrogenation of aromatic nitro compounds over the Ru/CN catalyst, and the direct pathway was proved to be dominant in catalyzing the intermediates. This journal is
- Yue, Shengnan,Wang, Xueguang,Li, Shaoting,Sheng, Yao,Zou, Xiujing,Lu, Xionggang,Zhang, Chunlei
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- Electrophilic bromination of meta-substituted anilines with N-bromosuccinimide: Regioselectivity and solvent effect
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N-Bromosuccinimide-mediated electrophilic aromatic bromination of a series of anilines substituted with an electron-with-drawing group in the meta position was investigated. The regioselectivity of the reaction is markedly dependent on the polarity of the solvent and the bromination reaction can be tuned by appropriate selection of the reaction medium. Georg Thieme Verlag Stuttgart.
- Bartoli, Sandra,Cipollone, Amalia,Squarcia, Antonella,Madami, Andrea,Fattori, Daniela
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- Preparation of Well-Ordered Mesoporous-Silica-Supported Ruthenium Nanoparticles for Highly Selective Reduction of Functionalized Nitroarenes through Transfer Hydrogenation
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MCM-41-type mesoporous silica (OMS-IL) was prepared by using an ionic liquid (1-hexadecyl-3-methylimidazolium bromide) as a template. The XRD and TEM results demonstrated that OMS-IL was more stable than the MCM-41 material. Ru nanoparticles were supported on OMS-IL (Ru/OMS-IL) by impregnating OMS-IL with a RuCl3 aqueous solution, and the resulting material was used for the selective reduction of nitroarenes. The effects of the components of the catalysts and the reaction conditions on the catalytic behavior of the prepared catalysts were investigated in detail. Ru/OMS-IL exhibited high catalytic activity and chemoselectivity for the reduction of various substituted nitroarenes to the corresponding aromatic amines in ethanol with hydrazine hydrate as a hydrogen donor under mild conditions. The Ru/OMS-IL catalysts were highly stable and could easily be recovered by simple filtration over at least six recycling reactions without any observable loss in catalytic performance.
- Wei, Ning,Zou, Xiujing,Huang, Haigen,Wang, Xueguang,Ding, Weizhong,Lu, Xionggang
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- N-doped graphitic carbon-improved Co-MoO3 catalysts on ordered mesoporous SBA-15 for chemoselective reduction of nitroarenes
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Metallic Co-MoO3 catalysts supported on ordered mesoporous SBA-15 were first prepared through in situ reaction of SBA-15-supported Co-Mo oxides with 1,10-phenanthroline. The resulting Co-MoO3/NC@SBA-15 catalysts with N-doped carbon (NC) exhibited high catalytic activity and chemoselectivity for selective reduction of various functionalized nitroarenes to the corresponding arylamines in ethanol with hydrazine hydrate at near room temperature (30 °C). For reduction of all tested substrates (28 examples), the catalyst could afford a conversion of >99% and arylamine selectivity of >99%. The excellent catalytic performance of the Co-MoO3/NC@SBA-15 was attributed to the Co-Nχ(C)-Mo active sites generated through the interaction between the surface Co-Nχ(C) and MoO3 species, promoting the dissociation of hydrazine molecule into the active H* species for the reduction of nitro groups. After the seventh cycle for reduction of 4-methoxylnitrobenzene, the 2%Co-MoO3/NC@SBA-15 showed little change in catalytic performance, textural properties, size and dispersion of metal species and valence states of elements, indicating high stability and recyclability.
- Huang, Haigen,Liang, Xiangcheng,Wang, Xueguang,Sheng, Yao,Chen, Chenju,Zou, Xiujing,Lu, Xionggang
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- Efficient and recyclable bimetallic Co–Cu catalysts for selective hydrogenation of halogenated nitroarenes
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Silica supported N-doped carbon layers encapsulating Co–Cu nanoparticles (Co1Cux@CN/SiO2) were prepared by a one-step impregnation of Co(NO3)2·6H2O, Cu(NO3)2·3H2O, urea and glucose, following in situ carbothermal reduction. Effects of Cu contents on the catalytic performance of the Co1Cux@CN/SiO2 catalysts were investigated for selective hydrogenation of p-chloronitrobenzene to p-chloroaniline. The Co1Cu0.30@CN/SiO2 with Cu/Co molar ratio of 0.30:1 presented much higher activity and stability than the monometallic Co@CN/SiO2 catalyst. The addition of Cu into Co1Cux@CN/SiO2 catalysts had favorable effects on the formation of highly active Co–N sites and N-doped carbon layer. The role of the N-doped carbon layer was to protect the Co from oxidation by air, and the Co1Cu0.30@CN/SiO2 could be reused for at least 12 cycles without decrease in catalytic efficiency. Mechanistic and in situ infrared studies revealed that the interaction effect between the Co and Cu atoms made the surface of Co highly electron rich, which decreased adsorption of halogen groups and resulting in the enhanced selectivity during chemoselective hydrogenation of halogenated nitroarenes for a wide scope of substrates.
- Lu, Xionggang,Ren, Jiaan,Sheng, Yao,Wang, Xueguang,Wu, Baoqin,Zou, Xiujing
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- Cyclic (Alkyl)(amino)carbene Ligand-Promoted Nitro Deoxygenative Hydroboration with Chromium Catalysis: Scope, Mechanism, and Applications
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Transition metal catalysis that utilizes N-heterocyclic carbenes as noninnocent ligands in promoting transformations has not been well studied. We report here a cyclic (alkyl)(amino)carbene (CAAC) ligand-promoted nitro deoxygenative hydroboration with cost-effective chromium catalysis. Using 1 mol % of CAAC-Cr precatalyst, the addition of HBpin to nitro scaffolds leads to deoxygenation, allowing for the retention of various reducible functionalities and the compatibility of sensitive groups toward hydroboration, thereby providing a mild, chemoselective, and facile strategy to form anilines, as well as heteroaryl and aliphatic amine derivatives, with broad scope and particularly high turnover numbers (up to 1.8 × 106). Mechanistic studies, based on theoretical calculations, indicate that the CAAC ligand plays an important role in promoting polarity reversal of hydride of HBpin; it serves as an H-shuttle to facilitate deoxygenative hydroboration. The preparation of several commercially available pharmaceuticals by means of this strategy highlights its potential application in medicinal chemistry.
- Zhao, Lixing,Hu, Chenyang,Cong, Xuefeng,Deng, Gongda,Liu, Liu Leo,Luo, Meiming,Zeng, Xiaoming
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supporting information
p. 1618 - 1629
(2021/01/25)
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- Method for preparing 2-bromo-5-fluoroaniline
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The invention discloses a method for preparing 2-bromo-5-fluoroaniline, belonging to the field of organic chemical synthesis. The preparation method comprises the following steps: with 4-fluoroanilineas a raw material, reacting 4-fluoroaniline with acetic anhydride to generate 4-fluoroacetanilide; performing nitrification; replacing acetamido groups with bromine; and reducing nitro groups. Thus,the 2-bromo-5-fluoroaniline with high yield and high purity is prepared. The method has the advantages of high product yield, high purity, easy availability of raw materials and simple operation, andis beneficial to industrial production.
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- In Situ Synthesized Silica-Supported Co@N-Doped Carbon as Highly Efficient and Reusable Catalysts for Selective Reduction of Halogenated Nitroaromatics
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Silica-supported Co@N-doped carbon (Co@CN/SiO2) catalysts were first prepared by a one-step impregnation with a mixed solution of cobalt nitrate, glucose and urea, followed by in situ carbonization and reduction. The Co@CN/SiO2 catalysts were investigated for the selective reduction of nitro aromatics to the corresponding anilines using hydrazine hydrate. The Co@CN/SiO2-500 carbonized at 500 °C exhibited the highest catalytic activity and excellent stability without any decay of activity after 6 cycles for the reduction of nitrobenzene. Both metallic Co atoms and Co?N species formed in the Co@CN/SiO2 catalysts were active, but the Co?N species were dominant active sites. The high activities of the Co@CN/SiO2 catalysts were attributed to the synergistic effect between the Co and N atoms, promoting heterolytic cleavage of hydrazine to form H+/H? pairs. Representative examples demonstrated that the Co@CN/SiO2-500 could completely transform various halogen-substituted nitro aromatics to the corresponding halogenated anilines with high TOFs and selectivity of '99.5 percent.
- Sheng, Yao,Wang, Xueguang,Yue, Shengnan,Cheng, Gonglin,Zou, Xiujing,Lu, Xionggang
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p. 4632 - 4641
(2020/07/30)
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- Synthesis method and intermediate for 2-bromo-5-fluoro-4-nitroaniline
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The invention discloses a synthesis method and an intermediate for 2-bromo-5-fluoro-4-nitroaniline. The synthesis method for 2-bromo-5-fluoro-4-nitroaniline comprises the step of carrying out a nitration reaction on 2-bromo-5-fluoroaniline and a nitration reagent to generate the 2-bromo-5-fluoro-4-nitroaniline, or comprises the following steps: reacting the 2-bromo-5-fluoroaniline with an amino protection reagent to obtain amino-protected 2-bromo-5-fluoroaniline, then carrying out the nitration reaction on the amino-protected 2-bromo-5-fluoroaniline and the nitration reagent to generate a nitration product that is the intermediate, and finally, removing the amino protection group from the nitration product to obtain the 2-bromo-5-fluoro-4-nitroaniline. The synthesis method has the advantages of high reaction yield, high product purity and easily available raw materials.
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Paragraph 0056-0060
(2020/01/12)
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- Direct Synthesis of Structurally Divergent Indole Alkaloids from Simple Chemicals
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A direct and structurally divergent synthesis of indole alkaloids from very simple 2-vinylanilines, alkynes and TBN via a novel substrate fragmentation/cycloaddition strategy has been developed, which provides an efficient noble-metal-free approach to access a library of highly valuable indole derivatives of tryptamines and tryptamine-related oximes, lactams, and lactones, as well as β-carbolines, spiroindolines, and hexa-hydropyrrolo[2,3-b]indoles.
- Shen, Tao,Zhu, Bencong,Lin, Fengguirong,Pan, Jun,Wei, Jialiang,Luo, Xiao,Liu, Jianzhong,Jiao, Ning
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supporting information
p. 815 - 818
(2018/07/31)
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- Reduction of organic azides to amines using reusable Fe3O 4 nanoparticles in aqueous medium
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Aromatic, heteroaromatic and sulfonyl azides were conveniently reduced to the corresponding amines in excellent yields using hydrazine hydrate in the presence of iron oxide nanoparticles. The Fe3O4-MNPs could be easily separated by an external magnet, and recycled ten times without significant loss of the catalytic efficiency. The Royal Society of Chemistry 2013.
- Pagoti, Sreenivasarao,Surana, Subham,Chauhan, Ajay,Parasar, Bibudha,Dash, Jyotirmayee
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p. 584 - 588
(2013/03/28)
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- CONSTRAINED COMPOUNDS AS CGRP-RECEPTOR ANTAGONISTS
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The invention encompasses constrained bicyclic and tricyclic CGRP-receptor antagonists, methods for identifying them, pharmaceutical compositions comprising them, and methods for their use in therapy for treatment of migraine and other headaches, neurogenic vasodilation, neurogenic inflammation, thermal injury, circulatory shock, flushing associated with menopause, airway inflammatory diseases, such as asthma and chronic obstructive pulmonary disease (COPD), and other conditions the treatment of which can be effected by the antagonism of CGRP-receptors.
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Page/Page column 95-96
(2008/06/13)
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- Constrained compounds as CGRP-receptor antagonists
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The invention encompasses constrained bicyclic and tricyclic CGRP-receptor antagonists, methods for identifying them, pharmaceutical compositions comprising them, and methods for their use in therapy for treatment of migraine and other headaches, neurogenic vasodilation, neurogenic inflammation, thermal injury, circulatory shock, flushing associated with menopause, airway inflammatory diseases, such as asthma and chronic obstructive pulmonary disease (COPD), and other conditions the treatment of which can be effected by the antagonism of CGRP-receptors.
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Page/Page column 61
(2008/06/13)
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- High affinity central benzodiazepine receptor ligands. Part 3: Insights into the pharmacophore and pattern recognition study of intrinsic activities of pyrazolo[4,3-c]quinolin-3-ones
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Novel 2-phenyl-2,5-dihydropyrazolo[4,3-c]quinolin-3-(3H)-ones (PQs) endowed with high affinity for central benzodiazepine receptor (BzR) were synthesized. In particular, 9-fluoro-2-(2-fluorophenyl)-2,5-dihydro-3H- pyrazolo[4,3-c]quinolin-3-one (22) showed binding affinity in the subnanomolar concentration range and proved to be in vitro a potent antagonist. This finding allowed the nature of the hydrogen bonding receptor site H 2 to be established, as located between the N-1 nitrogen of the PQ nucleus and the ortho position of the N-2-aryl group. [35S]tert- Butylbicyclophosphorothionate ([35S]TBPS) binding assays and electrophysiological measurements of the effects on GABA-evoked Cl- currents at recombinant human α1β2γ 2L GABAA receptors, expressed in Xenopus laevis oocytes, were used to assess the intrinsic activities of a large series of PQs. With the aim of extracting discriminant information and distinguishing BzR ligands with different profiles of efficacy, 51 PQ derivatives, including full and partial agonists, antagonists, and inverse agonists, were analyzed in a multidimensional chemical descriptor space, defined by the lipophilicity parameter CLOG P and 3-D molecular WHIM descriptors, by means of principal component analysis, k-nearest neighbors (k-NN) method, and linear discriminant analysis (LDA). The classification methods were applied to subsets of pairs of efficacy classes, and lipophilicity and 3-D size descriptors were detected as the discriminant variables by a stepwise linear discriminant analysis. LDA proved to be superior to k-NN, especially in classifying PQ ligands (60-84% of success in prediction ability) into categories of efficacies which were contiguous and quite overlapped in the hyperspace of variables.
- Carotti, Andrea,Altomare, Cosimo,Savini, Luisa,Chiasserini, Luisa,Pellerano, Cesare,Mascia, Maria P.,Maciocco, Elisabetta,Busonero, Fabio,Mameli, Manuel,Biggio, Giovanni,Sanna, Enrico
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p. 5259 - 5272
(2007/10/03)
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