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Chemoselective transfer hydrogenation to nitroarenes mediated by oxygen-implanted MoS2
We present an efficient approach for the chemoselective synthesis of arylamines from nitroarenes and formate over an oxygen-implanted MoS2 catalyst (O-MoS2). O-MoS2 was prepared by incomplete sulfidation and reduction of an ammonium molybdate precursor. A number of Mo–O bonds were implanted in the as-synthesized ultrathin O-MoS2 nanosheets. As a consequence of the different coordination geometries of O (MoO2) and S (MoS2), and lengths of the Mo–O and Mo–S bonds, the implanted Mo–O bonds induced obvious defects and more coordinatively unsaturated (CUS) Mo sites in O-MoS2, as confirmed by X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy, high resolution transmission electron microscopy, and extended X-ray absorption fine structure characterization of various MoS2-based materials. O-MoS2 with abundant CUS Mo sites was found to efficiently catalyze the chemoselective reduction of nitroarenes to arylamines.
Zhang, Chaofeng,Wang, Xu,Li, Mingrun,Zhang, Zhixin,Wang, Yehong,Si, Rui,Wang, Feng
p. 1569 - 1577
(2016)
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Palladium-catalyzed regioselective C2-arylation of 5-aminoindole
Pd(II)-catalyzed C-H arylations of 5-aminoindole using iodobenzenes as aryl source was studied. Despite pivalamide directing group at 5-position of the indole, the direct C2-arylation of the indole observed in high yields and with high regioselectivity.
Taskesenligil, Yunus,Lafzi, Ferruh,Kilic, Haydar,Saracoglu, Nurullah
p. 3289 - 3296
(2019)
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Aluminum Metal-Organic Framework-Ligated Single-Site Nickel(II)-Hydride for Heterogeneous Chemoselective Catalysis
The development of chemoselective and heterogeneous earth-abundant metal catalysts is essential for environmentally friendly chemical synthesis. We report a highly efficient, chemoselective, and reusable single-site nickel(II) hydride catalyst based on robust and porous aluminum metal-organic frameworks (MOFs) (DUT-5) for hydrogenation of nitro and nitrile compounds to the corresponding amines and hydrogenolysis of aryl ethers under mild conditions. The nickel-hydride catalyst was prepared by the metalation of aluminum hydroxide secondary building units (SBUs) of DUT-5 having the formula of Al(μ2-OH)(bpdc) (bpdc = 4,4′-biphenyldicarboxylate) with NiBr2 followed by a reaction with NaEt3BH. DUT-5-NiH has a broad substrate scope with excellent functional group tolerance in the hydrogenation of aromatic and aliphatic nitro and nitrile compounds under 1 bar H2 and could be recycled and reused at least 10 times. By changing the reaction conditions of the hydrogenation of nitriles, symmetric or unsymmetric secondary amines were also afforded selectively. The experimental and computational studies suggested reversible nitrile coordination to nickel followed by 1,2-insertion of coordinated nitrile into the nickel-hydride bond occurring in the turnover-limiting step. In addition, DUT-5-NiH is also an active catalyst for chemoselective hydrogenolysis of carbon-oxygen bonds in aryl ethers to afford hydrocarbons under atmospheric hydrogen in the absence of any base, which is important for the generation of fuels from biomass. This work highlights the potential of MOF-based single-site earth-abundant metal catalysts for practical and eco-friendly production of chemical feedstocks and biofuels.
Antil, Neha,Kumar, Ajay,Akhtar, Naved,Newar, Rajashree,Begum, Wahida,Dwivedi, Ashutosh,Manna, Kuntal
p. 3943 - 3957
(2021/04/12)

N-(3-cyano-1H-indol-5-yl)isonicotinamide and N-(3-cyano-1H-indol-5-yl)-1H-benzo[d]imidazole-5-carboxamide derivatives: Novel amide-based xanthine oxidase inhibitors
Our previous work demonstrated that amide is an efficient linker to explore chemical space of xanthine oxidase (XO) inhibitors that are entirely different from febuxostat and topiroxostat. In this effort, with 3-cyano-1H-indol-5-yl as a key moiety, two series of amide-based XO inhibitors, N-(3-cyano-1H-indol-5-yl)isonicotinamides (2a-w) and N-(3-cyano-1H-indol-5-yl)-1H-benzo[d]imidazole-5-carboxamides (3a-i), were designed and synthesized. The structure-activity relationship investigation identified N-(3-cyano-1-cyclopentyl-1H-indol-5-yl)-1H-benzo[d]imidazole-5-carboxamide (3i, IC50 = 0.62 μM) as the most promising compound, with 14.4-fold higher in vitro inhibitory potency than allopurinol (IC50 = 8.91 μM). Molecular simulations provided reasonable interaction modes for the representative compounds. Furthermore, in vivo activity evaluation demonstrated that compound 3i (oral dose of 12.8 mg/kg) has obviously hypouricemic effect on a potassium oxonate induced hyperuricemic rat model. Cytotoxicity assay and ADME prediction also supported that 3i is an excellent lead for further exploration of amide-based XO inhibitors.
Tu, Shun,Zhang, Ting-jian,Zhang, Yi,Zhang, Xu,Zhang, Zhen-hao,Meng, Fan-hao
(2021/07/31)

A novel water-dispersible and magnetically recyclable nickel nanoparticles for the one-pot reduction-Schiff base condensation of nitroarenes in pure water
In this work, a heterogeneous nanocatalyst called Ni-Fe3O4@Pectin~PPA ~ Piconal was first synthesized, which was investigated as a bifunctional catalyst containing nickel functional groups. On the other hand, this Ni-Fe3O4@Pectin~PPA ~ Piconal catalyst in aqueous solvents shows a very effective performance at ambient temperature for the nitroarene reduction reaction with sodium borohydride, for which NaBH4 is considered as a reducing agent. This is a novelty magnetic catalyst that was approved by various methods, including Fourier-transform infrared spectroscopy (FT-IR), X-ray powder diffraction (XRD), Dynamic light scattering (DLS), Transmission electron microscopy (TEM), vibrating sample magnetometer (VSM), Inductively coupled plasma (ICP), Energy-dispersive X-ray spectroscopy (EDX), and Field emission scanning electron microscopy (FESEM) analyses. From the satisfactory results obtained from the reduction of nitrogen, this catalytic system is used for a one-pot protocol containing a reduction-Schiff base concentration of diverse nitroarenes. It was corroborated with the heterogeneous catalytic experiments on the one-pot tandem synthesis of imines from nitroarenes and aldehydes. Finally, the novel Ni-Fe3O4@Pectin~PPA ~ Piconal catalyst could function as a more economically desirable and environmentally amicable in the catalysis field. The favorable products are acquired in good to high performance in the attendance of Ni-Fe3O4@Pectin~PPA ~ Piconal as a bifunctional catalyst. This catalyst can be recycled up to six steps without losing a sharp drop.
Ghamari Kargar, Pouya,Ravanjamjah, Asiye,Bagherzade, Ghodsieh
p. 1916 - 1933
(2021/07/10)

Cyclic (Alkyl)(amino)carbene Ligand-Promoted Nitro Deoxygenative Hydroboration with Chromium Catalysis: Scope, Mechanism, and Applications
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
supporting information
p. 1618 - 1629
(2021/01/25)

Calculated oxidation potentials predict reactivity in Baeyer-Mills reactions
Azobenzenes are widely used as dyes and photochromic compounds, with the Baeyer-Mills reaction serving as the most common method for their preparation. This transformation is often plagued by low yields due to the formation of undesired azoxybenzene. Here, we explore electronic effects dictating the formation of the azoxybenzene side-product. Using calculated oxidation potentials, we were able to predict reaction outcomes and improve reaction efficiency simply by modulating the oxidation potential of the arylamine component.
Gingrich, Phillip W.,Olson, David E.,Tantillo, Dean J.,Tombari, Robert J.,Tuck, Jeremy R.,Yardeny, Noah
supporting information
p. 7575 - 7580
(2021/09/22)

Development of potent dual PDK1/AurA kinase inhibitors for cancer therapy: Lead-optimization, structural insights, and ADME-Tox profile
We report the synthesis of novel first-in-class 2-oxindole-based derivatives as dual PDK1-AurA kinase inhibitors as a novel strategy to treat Ewing sarcoma. The most potent compound 12 is suitable for progression to in vivo studies. The specific attributes of 12 included nanomolar inhibitory potency against both phosphoinositide-dependent kinase-1 (PDK1) and Aurora A (AurA) kinase, with acceptable in vitro ADME-Tox properties (cytotoxicity in 2 healthy and 14 hematological and solid cancer cell-lines; inhibition of PDE4C1, SIRT7, HDAC4, HDAC6, HDAC8, HDAC9, AurB, CYP1A2, CYP2C9, CYP2C19, CYP2D6, and hERG). X-ray crystallography and docking studies led to the identification of the key AurA and PDK1/12 interactions. Finally, in vitro drug-intake kinetics and in vivo PK appear to indicate that these compounds are attractive lead-structures for the design and synthesis of PDK1/AurA dual-target molecules to further investigate the in vivo efficacy against Ewing Sarcoma.
Bacci, Andrea,Chiarugi, Sara,Gado, Francesca,Garau, Gianpiero,Gul, Sheraz,Huguet, Samuel,Manera, Clementina,Margheritis, Eleonora,Rapposelli, Simona,Rezai, Keyvan,Riveiro, Maria E.,Runfola, Massimiliano,Sestito, Simona,Vazquez, Ramiro
supporting information

(2021/10/08)

Method for preparing amine through catalytic reduction of nitro compound by cyclic (alkyl) (amino) carbene chromium complex
The cyclic (alkyl) (amino) carbene chromium complex is prepared from corresponding ligand salt, alkali and CrCl3 and used for catalyzing pinacol borane to reduce nitro compounds in an ether solvent under mild conditions to generate corresponding amine. The method for preparing amine has the advantages of cheap and accessible raw materials, mild reaction conditions, wide substrate application range, high selectivity and the like, and is simple to operate.
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(2021/04/17)

Copper(II) complex with oxazoline ligand: Synthesis, structures and catalytic activity for nitro compounds reduction
The Cu(II) complexes bearing bisoxazolines, tridentate pincer pybox and terpyridine ligands have been synthesized and fully characterized. The molecular structures of copper complexes 1a and 1c were confirmed by single-crystal X-ray diffraction methods. These copper complexes highly catalyzed nitro compounds reduction to aniline and its derivatives in the presence of NaBH4 reducing agent in water solvent. The complex 1e was an efficient catalyst toward nitro compounds reduction with wide functional group substrate scope and aliphatic nitro compounds.
Du, Jun,Gao, Li-Li,Jia, Wei-Guo,Li, Mei,Zhi, Xue-Ting
(2020/05/14)

Synthesis, characterization, and catalytic activity of half-sandwich ruthenium complexes with pyridine/phenylene bridged NHC = E (NHC = N-heterocyclic carbene, E = S, Se) ligands
Three half-sandwichruthenium(II) complexes with pyridine/phenylene bridged NHC = E (NHC = N-heterocyclic carbene, E = S, Se) ligands [Ru(p-cymene)L](PF6)1–2 (1a–1c, L = ligand) were synthesized and characterized. All ruthenium complexes were fully characterized by 1H and 13C NMR spectra, mass spectrometry, and single-crystalX-ray diffraction methods. Moreover, the half-sandwich ruthenium complexes with NHC = E ligands showed highly catalytic activities towards to the tandem dehydrogenation of ammonia borane (AB) and hydrogenation of R–NO2 to R–NH2 at 353 K in water.
Jia, Wei-Guo,Du, Teng-Teng,Gao, Li-Li,Du, Jun
(2020/05/16)

Commercially Available CuO Catalyzed Hydrogenation of Nitroarenes Using Ammonia Borane as a Hydrogen Source
Tandem ammonia borane dehydrogenation and nitroarenes hydrogenation has been reported as a novel strategy for the preparation of aromatic amines. However, the practical application of this strategy is subjected to the high-cost and tedious preparation of supported noble metal nanocatalysts. The commercially available CuO powder is herein demonstrated to be a robust catalyst for hydrogenation of nitroarenes using ammonia borane as a hydrogen source under mild conditions. Numerous amines (even sterically hindered, halogenated, and diamines) could be obtained through this method. This monometallic catalyst is characteristic of support-free, excellent chemoselectivity, low-cost, and high recyclability, which will favor its future utilization in preparative reduction chemistry. Mechanistic studies are also carried out to clarify that diazene and azoxybenzene are key intermediates of this heterogeneous reduction.
Du, Jialei,Chen, Jie,Xia, Hehuan,Zhao, Yiwei,Wang, Fang,Liu, Hong,Zhou, Weijia,Wang, Bin
p. 2426 - 2430
(2020/03/30)

Half-sandwich ruthenium complexes with Schiff base ligands bearing a hydroxyl group: Preparation, characterization and catalytic activities
Three half-sandwich ruthenium(II) complexes with hydroxyl group functionalized Schiff-base ligands [Ru(p-cymene)LCl] (2a-2c) have been synthesized and characterized. All ruthenium complexes were fully characterized by 1H and 13C NMR spectra, mass spectrometry and infrared spectrometry. The molecular structure of ruthenium complex 2c was confirmed by single-crystal X-ray diffraction methods. Furthermore, these half-sandwich ruthenium complexes were found to exhibit high catalytic activity for nitro compounds reduction using NaBH4 reducing agent in the presence of cetyltrimethylammonium bromide (CTAB) in water at room temperature.
Jia, Wei-Guo,Wang, Zhi-Bao,Zhi, Xue-Ting
(2019/11/20)

Ultrasound-assisted rapid reduction of nitroaromatics to anilines using gallium metal
The reduction of nitroaromatic compounds to anilines is widely used throughout organic synthesis. Typical methods of performing this transformation utilize hydrogenation over a pyrophoric catalyst or a finely divided reducing metal, which often affords heterogeneous mixtures that are difficult to purify. Herein, we report for the first time the use of gallium metal as a reducing agent in organic synthesis. The reaction proceeds under aerobic conditions and affords homogeneous mixtures for a convenient workup. Using this method, twelve anilines were obtained in 33% to quantitative yields with short reaction times of 10-60 minutes.
Bento, Ian,Bernaldez, Mabel,Noguchi, Ryden,Kawakami, Joel
supporting information
p. 1404 - 1407
(2020/03/31)

General and selective synthesis of primary amines using Ni-based homogeneous catalysts
The development of base metal catalysts for industrially relevant amination and hydrogenation reactions by applying abundant and atom economical reagents continues to be important for the cost-effective and sustainable synthesis of amines which represent highly essential chemicals. In particular, the synthesis of primary amines is of central importance because these compounds serve as key precursors and central intermediates to produce value-added fine and bulk chemicals as well as pharmaceuticals, agrochemicals and materials. Here we report a Ni-triphos complex as the first Ni-based homogeneous catalyst for both reductive amination of carbonyl compounds with ammonia and hydrogenation of nitroarenes to prepare all kinds of primary amines. Remarkably, this Ni-complex enabled the synthesis of functionalized and structurally diverse benzylic, heterocyclic and aliphatic linear and branched primary amines as well as aromatic primary amines starting from inexpensive and easily accessible carbonyl compounds (aldehydes and ketones) and nitroarenes using ammonia and molecular hydrogen. This Ni-catalyzed reductive amination methodology has been applied for the amination of more complex pharmaceuticals and steroid derivatives. Detailed DFT computations have been performed for the Ni-triphos based reductive amination reaction, and they revealed that the overall reaction has an inner-sphere mechanism with H2metathesis as the rate-determining step.
Beller, Matthias,Chandrashekhar, Vishwas G.,Jagadeesh, Rajenahally V.,Jiao, Haijun,Murugesan, Kathiravan,Wei, Zhihong
p. 4332 - 4339
(2020/05/18)

Zn(0)-Catalysed mild and selective hydrogenation of nitroarenes
The hydrogenation of nitroarenes is one of the most important strategies for the preparation of anilines. However, it is still a great challenge to develop mild and efficient synthetic routes toward aniline synthesis, particularly those employing both non-precious metal catalysts and low-pressure H2. Herein, we report a highly efficient protocol for the selective hydrogenation of nitroarenes in neutral H2O using H2 (1 atm) over a heterogeneous Zn(0) catalyst under mild conditions. The nitro groups of an array of nitroarenes can be converted into -NH2 with up to 99percent conversions and a selectivity of >99percent, even when functionalized with easily reducible substituents, or in the presence of aromatic ketones or styrene. This study might open an avenue for the selective hydrogenation of nitroarenes over a zinc catalyst using 1 atm H2.
Du, Muyao,Hu, Pan,Jv, Xinchun,Sun, Shuting,Wang, Bo,Zhang, Qun,Zhao, Ruixiang
supporting information
p. 4640 - 4644
(2020/08/10)

Nickel-Catalyzed Dehydrogenation of N-Heterocycles Using Molecular Oxygen
Herein, an efficient and selective nickel-catalyzed dehydrogenation of five- and six-membered N-heterocycles is presented. The transformation occurs in the presence of alkyl, alkoxy, chloro, free hydroxyl and primary amine, internal and terminal olefin, trifluoromethyl, and ester functional groups. Synthesis of an important ligand and the antimalarial drug quinine is demonstrated. Mechanistic studies revealed that the cyclic imine serves as the key intermediate for this stepwise transformation.
Banerjee, Debasis,Bera, Atanu,Bera, Sourajit
supporting information

(2020/09/02)

A new bifunctional heterogeneous nanocatalyst for one-pot reduction-Schiff base condensation and reduction-carbonylation of nitroarenes
In this work, synthesis of Pd-NHC-γ-Fe2O3-n-butyl-SO3H and its activity as a bifunctional heterogeneous nanocatalyst containing Pd-NHC and acidic functional groups, are described. This newly synthesized nanomagnetic catalyst is fully characterized by different methods such as FT-IR, XPS, TEM, VSM, ICP and TG analysis. At first, the catalytic activity of Pd-NHC-γ-Fe2O3-n-butyl-SO3H is evaluated for the reduction of nitroarenes in aqueous media using NaBH4 as a clean source of hydrogen generation at ambient temperature. Using the promising results obtained from the nitroarene reduction, this catalytic system is used for two one-pot protocols including reduction-Schiff base condensation and reduction-carbonylation of various nitroarenes. In these reactions the in situ formed amines are further reacted with aldehydes to yield imines or carbonylated to amides. The desired products are obtained in good to high yields in the presence of Pd-NHC-γ-Fe2O3-n-butyl-SO3H as a bifunctional catalyst. The catalyst is reused with the aid of a magnetic bar for up to six consecutive cycles without any drastic loss of its catalytic activity.
Sobhani, Sara,Chahkamali, Farhad Omarzehi,Sansano, José Miguel
p. 1362 - 1372
(2019/01/24)

Hydrogenation of nitroarenes to anilines in a flow reactor using polystyrene supported rhodium in a catalyst-cartridge (Cart-Rh@PS)
The present methodology described the chemo-selective hydrogenation of various nitroarenes in a flow reactor under polystyrene supported rhodium in a catalyst-cartridge (Cart-Rh@PS) as a heterogeneous nano-catalyst. The polystyrene supported Rh (Rh@PS) nanoparticles (NPs) were prepared by following our earlier reported protocol and packed inside the catalyst-cartridge (Cat-Cart) to obtain Cart-Rh@PS, which is compatible with ThalesNano's H-Cube Pro flow system. The advantages of the prepacked catalyst Cart-Rh@PS are as follows: no need for catalyst activation up to 12 runs, negligible metal leaching detected by ICP-AES analysis and significantly less back pressure generated under the flow conditions. The same catalyst, Cart-Rh@PS, was also effective up to a 1 gram scale for the reduction of nitroarenes and reusable for successive runs. The hydrogenation in the flow reactor is a greener approach for the reduction of nitroarenes to their corresponding anilines in high yields.
Sharma, Saurabh,Yamini,Das, Pralay
supporting information
p. 1764 - 1769
(2019/01/28)

Fe3O4 – Glutathione stabilized Ag nanoparticles: A new magnetically separable robust and facile catalyst for aqueous phase reduction of nitroarenes
The heterostructured Ag nanoparticles decorated Fe3O4 Glutathione (Fe3O4-Glu-Ag) nanoparticles (NPs) were synthesized by sonicating glutathione (Glu) with magnetite and further surface immobilization of silver NPs on it. The ensuing magnetic nano catalyst is well characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM), powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA). The prepared Fe3O4-Glu-Ag nanoparticles have proved to be an efficient and recyclable nanocatalyst with low catalyst loading for the reduction of nitroarenes and heteronitroarenes to respective amines in the presence of NaBH4 using water as a green solvent which could be easily separated at the end of a reaction using an external magnet and can be recycled up to 5 runs without any significant loss in catalytic activity. Gram scale study for the reduction of 4-NP has also being carried out successfully and it has been observed that this method can serve as an efficient protocol for reduction of nitroarenes on industrial level.
Kumari, Mitlesh,Gupta, Ragini,Jain, Yachana
(2019/09/09)

Utilization of a Hydrogen Source from Renewable Lignocellulosic Biomass for Hydrogenation of Nitroarenes
Exploring of hydrogen source from renewable biomass, such as glucose in alkaline solution, for hydrogenation reactions had been studied since 1860s. According to proposed pathway, only small part of hydrogen source in glucose was utilized. Herein, the utilization of a hydrogen source from renewable lignocellulosic biomass, one of the most abundant renewable sources in nature, for a hydrogenation reaction is described. The hydrogenation is demonstrated by reduction of nitroarenes to arylamines in up to 95 % yields. Mechanism studies suggest that the hydrogenation occurs via a hydrogen transformation pathway.
Tan, Fang-Fang,Tang, Kai-Li,Zhang, Ping,Guo, Yan-Jun,Qu, Mengnan,Li, Yang
p. 4189 - 4195
(2019/03/07)

Switchable Bifunctional Bistate Reusable ZnO-Cu for Selective Oxidation and Reduction Reaction
Herein we disclosed the utilization of copper loaded zinc oxide (ZnO-Cu) for its stimuli (O2/light) responsive switchable performance between its reduced (S-1) and oxidized (S-2) state for two antagonistic reactions, namely oxidation of alkyl arenes/heteroarenes to aldehydes/ketones and reduction of nitro arenes/heteroarenes to corresponding amines. The two states of the catalyst showed its switchable performance as highly active and poorly active catalyst for oxidation and reduction, and both reactions could be turned "off" and "on" by changing the stimuli (light and O2/N2). The switching efficiency between the states and their relative reactivity were found to be consistent under variety of reaction conditions and remain unaltered irrespective of oxidation-reduction (or vice versa) sequence and substrates used in the reaction. The photo catalysts (S-1 and S-2) demonstrated good catalytic activity, multiple reusability, broad substrate scope, and reasonable functional group tolerance for both the reactions and probed its quality performance in a large-scale setup. The system was used in an assisted tandem catalysis setup for the synthesis of benzyl amines utilizing both oxidation and reduction reaction by stimuli responsive switching between the states of the catalyst.
Sarmah, Kasturi,Mukhopadhyay, Subhamoy,Maji, Tarun K.,Pratihar, Sanjay
p. 732 - 745
(2019/01/11)

INHIBITORS OF HEPATITIS C VIRUS REPLICATION
The present invention relates to compounds of formula (I) that are useful as hepatitis C virus (HCV) NS5A inhibitors, the synthesis of such compounds, and the use of such compounds for inhibiting HCV NS5A activity, for treating or preventing HCV infections and for inhibiting HCV viral replication and/or viral production in a cell-based system.
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(2019/05/15)

A ruthenium bisoxazoline complex as a photoredox catalyst for nitro compound reduction under visible light
An unreported ruthenium(ii) complex containing bisoxazoline ligands has been synthesized and characterized. To test the catalytic ability of the ruthenium complex, the synthesis of anilines from nitro compounds in the presence of a mild reducing agent sodium borohydride and visible light has been developed. Mechanistic studies involving the experiment and DFT calculations suggest that the reaction could involve a radical pathway with the assistance of a photoredox catalyst.
Jia, Wei-Guo,Cheng, Ming-Xia,Gao, Li-Li,Tan, Siu Min,Wang, Chao,Liu, Xiaogang,Lee, Richmond
supporting information
p. 9949 - 9953
(2019/07/15)

Direct conversion of phenols into primary anilines with hydrazine catalyzed by palladium
Primary anilines are essential building blocks to synthesize various pharmaceuticals, agrochemicals, pigments, electronic materials, and others. To date, the syntheses of primary anilines mostly rely on the reduction of nitroarenes or the transition-metal-catalyzed Ullmann, Buchwald-Hartwig and Chan-Lam cross-coupling reactions with ammonia, in which non-renewable petroleum-based chemicals are typically used as feedstocks via multiple step syntheses. A long-standing scientific challenge is to synthesize various primary anilines directly from renewable sources. Herein, we report a general method to directly convert a broad range of phenols into the corresponding primary anilines with the cheap and widely available hydrazine as both amine and hydride sources with simple Pd/C as the catalyst.
Qiu, Zihang,Lv, Leiyang,Li, Jianbin,Li, Chen-Chen,Li, Chao-Jun
p. 4775 - 4781
(2019/05/16)

Supported Rhodium Nanoparticles Catalyzed Reduction of Nitroarenes, Arylcarbonyls and Aryl/Benzyl Sulfoxides using Ethanol/Methanol as In Situ Hydrogen Source
A facile reduction reaction of nitroarenes, aryl carbonyls and aryl/benzyl sulfoxides was performed under polystyrene supported rhodium (Rh@PS) catalyzed conditions using ethanol/methanol as in situ hydrogen source. The catalyst Rh@PS played a pivotal role in the oxidation of ethanol/methanol in the presence of traces of aerial oxygen and base to produce hydrogen gas, enough for further reduction reaction. Transmission electron microscopy (TEM) analysis indicated that the average particle size of the Rh nanoparticles (NPs) lies between 2–3 nm; this is responsible for its high catalytic activity. The advantages of Rh@PS are its catalytic activity, easy preparation, recovery, recyclability for several runs, and low metal leaching during reaction. (Figure presented.).
Sharma, Saurabh,Bhattacherjee, Dhananjay,Das, Pralay
supporting information
p. 2131 - 2137
(2018/04/17)

Textile-supported silver nanoparticles as a highly efficient and recyclable heterogeneous catalyst for nitroaromatic reduction at room temperature
A novel textile-based nanosilver catalyst was prepared with a facile synthetic method. The textile-supported nanosilver (TsNS) proved to be an excellent heterogeneous catalyst for the reduction of nitroaromatics with a broad substrate scope. It can be recycled for up to 6 times without significantly compromising its catalytic efficacy. The TsNS catalyst was developed into a column reactor, demonstrating its practical application with the advantages of low cost, ease of operation and large scale synthesis capabilities. Scanning electron microscopy (SEM) showed that there were few changes to the catalyst's surface after the reaction. Besides, inductively coupled plasma (ICP) analysis showed that few silver particles leaked, and the interactions between the nitro groups of the nitroaromatics and the nanosilver particles were characterized by X-ray photoelectron spectroscopy (XPS), which lead to the proposal of a four-step mechanism for the reduction reaction.
Feng, Wei,Huang, Tingting,Gao, Liqian,Yang, Xianfeng,Deng, Wenbin,Zhou, Rui,Liu, Hongjun
p. 6288 - 6292
(2018/02/19)

Highly efficient nitrobenzene and alkyl/aryl azide reduction in stainless steel jars without catalyst addition
The mechanochemical and selective reduction of aryl nitro and aryl/alkyl azide derivatives, with either formate salts or hydrazine, to the corresponding, synthetically useful amines occurs in excellent yields in a planetary ball mill without the addition of a catalyst. This newly developed and solvent-free protocol is efficient, fast and does not require the addition of a metal hydrogenation catalyst as the stainless steel jar itself fulfils that role. The method has been applied to a broad range of compounds and excellent yields have been obtained. The formylation of alkyl amines has been successfully performed, by means of mechanochemical activation, in the presence of ammonium formate alone.
Martina, Katia,Baricco, Francesca,Tagliapietra, Silvia,Moran, Maria Jesus,Cravotto, Giancarlo,Cintas, Pedro
supporting information
p. 18881 - 18888
(2018/11/26)

Cobalt-based nanoparticles prepared from MOF-carbon templates as efficient hydrogenation catalysts
The development of efficient and selective nanostructured catalysts for industrially relevant hydrogenation reactions continues to be an actual goal of chemical research. In particular, the hydrogenation of nitriles and nitroarenes is of importance for the production of primary amines, which constitute essential feedstocks and key intermediates for advanced chemicals, life science molecules and materials. Herein, we report the preparation of graphene shell encapsulated Co3O4- and Co-nanoparticles supported on carbon by the template synthesis of cobalt-terephthalic acid MOF on carbon and subsequent pyrolysis. The resulting nanoparticles create stable and reusable catalysts for selective hydrogenation of functionalized and structurally diverse aromatic, heterocyclic and aliphatic nitriles, and as well as nitro compounds to primary amines (>65 examples). The synthetic and practical utility of this novel non-noble metal-based hydrogenation protocol is demonstrated by upscaling several reactions to multigram-scale and recycling of the catalyst.
Murugesan, Kathiravan,Senthamarai, Thirusangumurugan,Sohail, Manzar,Alshammari, Ahmad S.,Pohl, Marga-Martina,Beller, Matthias,Jagadeesh, Rajenahally V.
p. 8553 - 8560
(2018/11/30)

Half-Sandwich Ruthenium Phenolate-Oxazoline Complexes: Experimental and Theoretical Studies in Catalytic Transfer Hydrogenation of Nitroarene
In this work, five ruthenium complexes [Ru(p-cymene)LCl] containing phenolate-oxazoline ligands [L = 2-(4,5-dihydrooxazol-2-yl)phenol (1); L = 2-(4-methyl-4,5-dihydrooxazol-2-yl)phenol (2); L = 2-(4-ethyl-4,5-dihydrooxazol-2-yl)phenol (3); L = 2-(4-phenyl-4,5-dihydrooxazol-2-yl)phenol (4); and 2-(4,4-dimethyl-4,5-dihydrooxazol-2-yl)phenol (5)] were synthesized and characterized. The solid-state structures of all ruthenium complexes were determined by single-crystal X-ray diffraction. The catalytic activities of these complexes in the transfer hydrogenation reaction of nitroarene to aniline were investigated. Aniline and their derivatives were obtained in good to excellent yields with isopropanol as the hydride source. The present protocol provides an environmentally benign synthetic method for the reduction of nitroarenes to anilines without employing harsh reaction conditions. Theoretical studies employing density functional theory were carried with the aim to propose a feasible reaction mechanism and to draw insights into the reactivity of the half-sandwich ruthenium catalyst.
Jia, Wei-Guo,Ling, Shuo,Zhang, Hai-Ning,Sheng, En-Hong,Lee, Richmond
p. 40 - 47
(2018/01/17)

Unravelling 2-aminoquinazolin-4(3: H)-one as an organocatalyst for the chemoselective reduction of nitroarenes
A novel, mild and transition metal-free, 2-aminoquinazolin-4(3H)-one-assisted reduction of nitroarenes employing hydrazine hydrate as reducing agent and potassium carbonate as a base is reported. For the first time, the activation of hydrazine hydrate with an organocatalyst has been explored for reduction reactions. Also for the first time, 2-aminoquinazolin-4(3H)-one and its derivatives have been investigated as hydrogen bonding organocatalysts for the reduction of nitroarenes to anilines. Sensitive functional groups such as sulfonamide, carboxyl, amide and halides were well tolerated in this green methodology with scalability and high chemoselectivity.
Thakur, Maheshwar S.,Nayal, Onkar S.,Rana, Rohit,Kumar, Manoranjan,Sharma, Sushila,Kumar, Neeraj,Maurya, Sushil K.
supporting information
p. 1373 - 1378
(2018/02/06)

Discovery of the cancer cell selective dual acting anti-cancer agent (Z)-2-(1H-indol-3-yl)-3-(isoquinolin-5-yl)acrylonitrile (A131)
Selective targeting of cancer cells over normal cells is a key objective of targeted therapy. However few approaches achieve true mechanistic selectivity resulting in debilitating side effects and dose limitation. In this work we describe the discovery of A131 (4a), a new agent with an unprecedented dual mechanism of action targeting both mitosis and autophagy. Compound 4a was first identified in a phenotypic screen in which HeLa cells treated with 4a manifested mitotic arrest along with formation of multiple vesicles. Further investigations showed that 4a causes an increase in mitotic marker pH3 and autophagy marker LC3. Importantly 4a induces cell death in cancer cells while sparing normal cells which regrow after 4a is removed. Dual activities against pH3 and LC3 markers are required for cancer cell selectivity. An extensive SAR investigation confirmed 4a as the optimal dual inhibitor with potency against a panel of 30 cancer cell lines (average antiproliferative GI50 1.5 μM). In a mouse model of paclitaxel-resistant colon cancer, 4a showed 74% tumor growth inhibition when administered at a dose of 20 mg/kg IP twice a day.
See, Cheng Shang,Kitagawa, Mayumi,Liao, Pei-Ju,Lee, Kyung Hee,Wong, Jasmine,Lee, Sang Hyun,Dymock, Brian W.
p. 344 - 367
(2018/07/25)

Design, synthesis, and biological evaluation of new B-RafV600E kinase inhibitors
The association of deregulated signal pathways with various diseases has long been a research hotspot. One of the most important signal pathways, the MAPK (mitogen-activated protein kinase) signal pathway, plays a vital role in transducing extracellular signals into vital intracellular mechanisms. While mutations on its key component Raf kinase lead to sever diseases, targeted inhibition has thereby become an attractive therapeutic strategy. Several drugs have been approved for the treatment of Raf relevant diseases, yet more candidates are ever needed as the known drugs have confronted resistance and side effects. In the present study, we primarily investigated the binding modes of type I/II and type II inhibitors with B-Raf kinase. Based on the current knowledge, these ligands were fragmented and recombined to provide new interesting insights. Afterwards, a series of derivatives has been synthesized after the validation of hit compound. In addition, in vitro assays were carried out to profile the pharmacological properties of all the entities. Of all the compounds, compound 5h showed the best profile and may be used in the future study.
Wang, Peng-Fei,Zhang, Yong-Jiao,Wang, Dong,Hu, Hui-Min,Wang, Zhong-Chang,Xu, Chen,Qiu, Han-Yue,Zhu, Hai-Liang
p. 2372 - 2380
(2018/03/29)

Chemoselective hydrogenation of unsaturated nitro compounds to unsaturated amines by Ni-Sn alloy catalysts
Ni-Sn alloy catalysts were prepared and applied to the hydrogenation of 4-nitrostyrene at 383423 K using H2 gas as the hydrogen donor. Ni3Sn2 alloy showed a significantly high conversion and selectivity towards 4-aminostyrene (Conv. 100%, Sel. 99%). Various unsaturated nitro compounds were also successfully converted into their corresponding unsaturated amines.
Yamanaka, Nobutaka,Hara, Takayoshi,Ichikuni, Nobuyuki,Shimazu, Shogo
p. 971 - 974
(2018/08/24)

A capping agent dissolution method for the synthesis of metal nanosponges and their catalytic activity towards nitroarene reduction under mild conditions
We report a general strategy for the synthesis of metal nanosponges (M = Ag, Au, Pt, Pd, and Cu) using a capping agent dissolution method where addition of water to the M@BNHx nanocomposite affords the metal nanosponges. The B-H bond of the BNHx polymer gets hydrolysed upon addition of water and produces hydrogen gas bubbles which act as dynamic templates leading to the formation of nanosponges. The rate of B-H bond hydrolysis has a direct impact on the final nanostructure of the materials. The metal nanosponges were characterized using powder XRD, electron microscopy, XPS, and BET surface area analyzer techniques. The porous structure of these nanosponges offers a large number of accessible surface sites for catalytic reactions. The catalytic activity of these metal nanosponges has been demonstrated for the reduction of 4-nitrophenol where palladium exhibits the highest catalytic activity (k = 0.314 min?1). The catalytic activity of palladium nanosponge was verified for the tandem dehydrogenation of ammonia borane and the hydrogenation of nitroarenes to arylamines in methanol at room temperature. The reduction of various substituted nitroarenes was proven to be functional group tolerant except for a few halogenated nitroarenes (X = Br and I) and >99% conversion was noted within 30-60 min with high turnover frequencies (TOF) at low catalyst loading (0.1 mol%). The catalyst could be easily separated out from the reaction mixture via centrifugation and was recyclable over several cycles, retaining its porous structure.
Ghosh, Sourav,Jagirdar, Balaji R.
p. 17401 - 17411
(2019/01/03)

STABILIZATION OF ACTIVE METAL CATALYSTS AT METAL-ORGANIC FRAMEWORK NODES FOR HIGHLY EFFICIENT ORGANIC TRANSFORMATIONS
Metal-organic framework (MOFs) compositions based on post?synthetic metalation of secondary building unit (SBU) terminal or bridging OH or OH2 groups with metal precursors or other post-synthetic manipulations are described. The MOFs provide a versatile family of recyclable and reusable single-site solid catalysts for catalyzing a variety of asymmetric organic transformations, including the regioselective boryiation and siiylation of benzyiic C—H bonds, the hydrogenation of aikenes, imines, carbonyls, nitroarenes, and heterocycles, hydroboration, hydrophosphination, and cyclization reactions. The solid catalysts can also be integrated into a flow reactor or a supercritical fluid reactor.
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Paragraph 0354-0356; 0359

(2019/01/07)

Metal-free deoxygenation and reductive disilylation of nitroarenes by organosilicon reducing reagents
A metal-free deoxygenation and reductive disilylation of nitroarenes was achieved using N,N’-bis(trime-thylsilyl)-4,4’-bipyridinylidene (1) under mild and neutral reaction conditions, and a broad functional group tolerance was possible in this reaction. Mono-deoxygenation, giving a synthetically valuable N,O-bis(trimethylsilyl)phe-nylhydroxylamine (7a) as a readily available and safe phenylnitrene source from nitrobenzene, and double-deoxy-genation, giving N,N-bis(trimethylsilyl)anilines 8, were easily controlled by varying the amounts of 1 and reaction temperature as well as adding dibenzothiophene (DBTP). Reaction of 2-arylnitrobenzenes with 1 resulted in the formation of the corresponding carbazoles 14 via in situ-gen-erated phenylnitrene species derived by thermolysis of N,O-bis(trimethylsilyl)phenylhydroxylamines 7, followed by their subsequent intramolecular C H insertion. In addition, the intramolecular N N coupling reaction proceeded in the reduction of 2,2’-dinitrobiphenyl derivatives by 1, giving the corresponding benzo[c]cinnolines.
Bhattacharjee, Argha,Hosoya, Hiromu,Ikeda, Hideaki,Nishi, Kohei,Tsurugi, Hayato,Mashima, Kazushi
supporting information
p. 11278 - 11282
(2018/10/20)

A 4, 4 - dimethoxy - 2, 2 - bipyridyl silver catalytic hydrogenation of aromatic nitro compound synthesis of aromatic amines (by machine translation)
The invention discloses a 4, 4 - dimethoxy - 2, 2 - bipyridyl silver catalytic hydrogenation of aromatic nitro compound synthesis of aromatic amines, the method uses a cheap, easy synthesis of 4, 4 - dimethoxy - 2, 2 - bipyridyl silver as catalyst, in order to green, environmental protection, non-toxic as the hydrogen source, the aromatic nitro compound in the relatively mild reaction conditions, one-step reaction can synthesize aromatic amine. The invention has simple operation, catalyst is cheap and easy and small consumption, mild reaction conditions, to substrate demonstrates better functional group tolerant, high product yield, industrial manufacturing cost, it has very good application prospect. (by machine translation)
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Paragraph 0016; 0029; 0032

(2017/07/19)

Single-Site Cobalt Catalysts at New Zr12(μ3-O)8(μ3-OH)8(μ2-OH)6 Metal-Organic Framework Nodes for Highly Active Hydrogenation of Nitroarenes, Nitriles, and Isocyanides
We report here the synthesis of a robust and porous metal-organic framework (MOF), Zr12-TPDC, constructed from triphenyldicarboxylic acid (H2TPDC) and an unprecedented Zr12 secondary building unit (SBU): Zr12(μ3-O)8(μ3-OH)8(μ2-OH)6. The Zr12-SBU can be viewed as an inorganic node dimerized from two commonly observed Zr6 clusters via six μ2-OH groups. The metalation of Zr12-TPDC SBUs with CoCl2 followed by treatment with NaBEt3H afforded a highly active and reusable solid Zr12-TPDC-Co catalyst for the hydrogenation of nitroarenes, nitriles, and isocyanides to corresponding amines with excellent activity and selectivity. This work highlights the opportunity in designing novel MOF-supported single-site solid catalysts by tuning the electronic and steric properties of the SBUs.
Ji, Pengfei,Manna, Kuntal,Lin, Zekai,Feng, Xuanyu,Urban, Ania,Song, Yang,Lin, Wenbin
p. 7004 - 7011
(2017/05/31)

Biomass-Derived Catalysts for Selective Hydrogenation of Nitroarenes
Development of catalytically active materials from biowaste represents an important aspect of sustainable chemical research. Three heterogeneous materials were synthesized from inexpensive biomass-based chitosan and abundant Co(OAc)2 using complexation followed by pyrolysis at various temperatures. These materials were applied in the catalytic hydrogenation of nitroarenes using molecular hydrogen. A variety of diversely functionalized nitroarenes including some pharmaceutically active compounds were converted into aromatic amines in high yields, with high selectivity, and with excellent functional group tolerance. This green protocol has also been implemented for the synthesis of a biologically important TRPC3 inhibitor.
Sahoo, Basudev,Formenti, Dario,Topf, Christoph,Bachmann, Stephan,Scalone, Michelangelo,Junge, Kathrin,Beller, Matthias
p. 3035 - 3039
(2017/08/18)

Hexafluoro-2-propanol-assisted quick and chemoselective nitro reduction using iron powder as catalyst under mild conditions
Hexafluoro-2-propanol as the promoter for the quick nitro reduction using a combination of iron powder and 2 N HCl aqueous solution is reported. This methodology has several positive features, as it is of room temperature, remarkably short reaction time. A wide range of substrates including those bearing reducible functional groups such as aldehyde, ketone, acid, ester, amide, nitrile, halogens, even allyl, propargyl and heterocycles are chemoselectively reduced in good to excellent yields, even on gram scale. Notably, the highly selective reduction of 3-nitrophenylboronic acid is achieved quantitatively. The reduction is also tolerant of common protecting groups, and aliphatic nitro compound, 1-nitrooctane can be reduced successfully.
Chen, Xu-Ling,Ai, Bai-Ru,Dong, Yu,Zhang, Xiao-Mei,Wang, Ji-Yu
supporting information
p. 3646 - 3649
(2017/08/23)

Base-Free Transfer Hydrogenation of Nitroarenes Catalyzed by Micro-Mesoporous Iron Oxide
An efficient and practical protocol for the transfer hydrogenation of nitroarenes was developed, which uses flower-shaped micro-mesoporous iron oxide (MMIO) with formic acid as the reducing agent and tris[(2-diphenylphosphino)-ethyl]phosphine as the ligand in the absence of an additional base. The recyclable catalytic system enables the reduction of the nitro group in a broad range of substrates to yield valuable amines and shows a high tolerance to sensitive functional groups.
Datta, Kasibhatta J.,Rathi, Anuj K.,Gawande, Manoj B.,Ranc, Vaclav,Zoppellaro, Giorgio,Varma, Rajender S.,Zboril, Radek
p. 2351 - 2355
(2016/07/28)

Chemoselective transfer hydrogenation of nitroarenes by highly dispersed Ni-Co BMNPs
Highly dispread Ni-Co bimetallic nanoparticles (Ni-Co BMNPs) are synthesized and applied as an efficient catalyst in the chemoselective transfer hydrogenation of nitroarenes (CTH) using hydrazine hydrate as the hydrogen donor. The BMNPs can efficiently catalyze the reduction reaction without any additives under mild conditions with high TOF. Significantly higher activity is achieved when compared with corresponding single-component catalysts, optimal composition of the Ni-Co BMNPs was screened which was proved to be crucial in both the selectivity and yields. Excellent performance of Ni-Co BMNPs can be ascribed to the improved dispersion of active sites on the BMNPs surface (compared with Ni NPs) and the electron transfer from cobalt to nickel.
Zhang, Jia-Wei,Lu, Guo-Ping,Cai, Chun
p. 25 - 29
(2016/06/13)

SELECTIVE ANTI-CANCER COMPOUNDS
A compound of formula I, wherein the compound of formula I has the structure: wherein R1 to R5, Y, L, Z and X1 to X7 have meanings given in the description, said compounds having utility in the treatment of hyperproliferative disease.
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Page/Page column 93

(2017/01/31)

Transfer hydrogenation of nitroarenes with hydrazine at near-room temperature catalysed by a MoO2 catalyst
We present an experimental and computational study of the elementary steps of hydrazine hydrogen transfer on crystalline MoO2, and demonstrate its unique bifunctional metallic-basic properties in a catalytic hydrogenation reaction. Density functional theory (DFT) calculations suggest that the stepwise hydrogen transfer via the prior cleavage of the N-H bond rather than the N-N bond, is the key step to create the dissociated hydride and proton species on the dual Mo and O sites, marking its difference with common oxides. Crystalline MoO2 shows exceptionally high chemoselectivity toward the nitro reduction over C=C, C≡C, and C≡N groups at room temperature and lower, down to 0 °C, rendering it as a promising catalytic material for hydrogenation reactions.
Zhang, Chaofeng,Lu, Jianmin,Li, Mingrun,Wang, Yehong,Zhang, Zhe,Chen, Haijun,Wang, Feng
p. 2435 - 2442
(2016/05/19)

Transfer hydrogenation of nitroarenes to arylamines catalysed by an oxygen-implanted MoS2 catalyst
We present an efficient approach for chemoselective synthesis of various functionalized arylamines from nitroarenes over an oxygen-implanted MoS2 catalyst (O-MoS2). The HRTEM, XRD, XPS, Raman, EXAFS and NH3-TPD characterizations show the existence of MoIVOx structure and abundant coordinative unsaturated (CUS) Mo sites in the 2D-layer structure of O-MoS2. In the transfer hydrogenation of nitroarenes with hydrazine hydrate, the MoIVOx structure works as the catalytic active center. The N2H4 selectively decomposes to the active hydrogen species in polar electronic states (Hδ? and Hδ+), which show high chemoselectivity toward the nitro reduction over [Formula presented], [Formula presented], and [Formula presented] groups. The O-MoS2 catalyst can be recovered in a facile manner from the reaction mixture and recycled four times without any significant loss of activity.
Zhang, Chaofeng,Zhang, Zhixin,Wang, Xu,Li, Mingrun,Lu, Jianmin,Si, Rui,Wang, Feng
p. 85 - 93
(2016/07/25)

Magnetic NiO nanoparticles confined within open ends MWCNTs: A novel and highly active catalyst for hydrogenation and synthesis of imines
A new nanocatalyst has been synthesized by confining magnetic nickel nanoparticles within carbon nanotubes (CNTs) and characterized by XRD, TEM, Raman and VSM. The character of the nanocatalyst passivated with a gas mixture was that it can be stored safely in air below 150 °C and needs no activation prior to use. In the catalytic test, a nickel oxide nanocatalyst confined inside the Multi-walled carbon nanotubes nanochannels (NiO/MWCNTs-in) was found to be a highly efficient and reusable catalyst for the reduction of various aromatic nitro compounds to various aromatic amines, the conversion and selectivity of which were almost up to 100% and exceed 80%. The prominent merit of the catalyst is that the overall formation rate of product inside the nanotubes exceeds that outside. Moreover, it is inexpensive, and could be prepared and scaled up easily. Besides, it can be simply separated from the reaction mixtures by an external magnetic field As a result of the possible confinement effect of CNTs, the employment of the CNTs channels as nanoreactors for catalysis may provide opportunities for the development of new heterogeneous catalysts.
Chen, Gangquan,Gao, Wenbin,Wang, Xuejun,Huo, Hongfei,Li, Wenzhu,Zhang, Le,Li, Rong,Li, Zuixiong
p. 58805 - 58812
(2016/07/06)

Method for preparing aromatic amine by aqueous reduction of aromatic compounds with nitro-substitution
The invention relates to a method for preparing aromatic amine by aqueous reduction of aromatic compounds with nitro-substitution. The aromatic compounds with nitro-substitution is dispersed in an aqueous solution containing a phase-transfer catalyst, prepared oxygen doped molybdenum disulfide which is used as a catalyst is added, in a condition at 100-160 DEG C, formic acid and formates which are used as reducing agents are used for reducing nitro compounds with high selectivity into corresponding aromatic amine substances. The method relates to a method for preparing aniline by reduction of nitrobenzene. The method has the advantages of good selectivity, mild conditions, and environment-friendly characteristics, and the method has a certain industrial application value.
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Paragraph 0076; 0077

(2016/12/01)

Selective hydrogenation method, catalyst used for the method
PROBLEM TO BE SOLVED: To provide a selective hydrogenation method for selectively hydrogenating, into amino groups with high efficiency, nitro groups of an aromatic compound including carbon-carbon double bonds and nitro groups and a selective hydrogenation method for selectively hydrogenating, into hydroxyl groups, aldehyde groups of a terpenoid including carbon-carbon double bonds and aldehyde groups.SOLUTION: The provided selective hydrogenation method of an aromatic compound including carbon-carbon double bonds and nitro groups or a terpenoid including carbon-carbon double bonds and aldehyde groups features the contact, with a hydrogen gas in the presence of a silver-cerium oxide composite comprising silver component particles and cerium oxide supported on surfaces of the silver component particles within a liquid phase including an organic solvent, of an aromatic compound including carbon-carbon double bonds and nitro groups or a terpenoid including carbon-carbon double bonds and aldehyde groups so as to induce a selective hydrogenation and conversion, into amino groups or hydroxyl groups, of the nitro groups included within the aromatic compound or aldehyde groups included within the terpenoid.
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Paragraph 0080-0081

(2017/05/02)

Dual optimization approach to bimetallic nanoparticle catalysis: Impact of M1/M2 ratio and supporting polymer structure on reactivity
A dual optimization approach to nanoparticle catalysis is reported in which both the composition of a bimetallic nanoparticle and the electronic properties of the supporting polystyrene-based polymer can be varied to optimize reactivity and chemoselectivity in nitroarene reductions. Ruthenium-cobalt nanoparticles supported on polystyrene are shown to catalyze nitroarene reductions at room temperature with exceptional activity, as compared with monometallic ruthenium catalysts. Both the identity of the second metal and the M1/M2 ratio show a profound effect on the chemoselectivity of nitroarene reductions. These polymer-supported bimetallic catalysts are shown to react with nearly complete chemoselectivity for nitro group reduction over a variety of easily reducible functional groups. The electronic properties of the supporting polymer also have a significant impact on catalysis, in which electron-deficient polystyrenes enable 100% conversion to the aniline product in just 20 min at room temperature. Polymer effects are also shown to influence the mechanism of the reduction reaction, in addition to accelerating the rate, confirming the impact of the polymer structure on catalytic efficiency. These catalysts are easily prepared in a single step from commercial materials and can be readily recycled without loss of activity.
Udumula, Venkatareddy,Tyler, Jefferson H.,Davis, Donald A.,Wang, Hao,Linford, Matthew R.,Minson, Paul S.,Michaelis, David J.
p. 3457 - 3462
(2015/06/16)