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A ternary Cu2O-Cu-CuO nanocomposite: A catalyst with intriguing activity
In this work, the syntheses of Cu2O as well as Cu(0) nanoparticle catalysts are presented. Copper acetate monohydrate produced two distinctly different catalyst particles with varying concentrations of hydrazine hydrate at room temperature without using any surfactant or support. Then both of them were employed separately for 4-nitrophenol reduction in aqueous solution in the presence of sodium borohydride at room temperature. To our surprise, it was noticed that the catalytic activity of Cu2O was much higher than that of the metal Cu(0) nanoparticles. We have confirmed the reason for the exceptionally high catalytic activity of cuprous oxide nanoparticles over other noble metal nanoparticles for 4-nitrophenol reduction. A plausible mechanism has been reported. The unusual activity of Cu2O nanoparticles in the reduction reaction has been observed because of the in situ generated ternary nanocomposite, Cu2O-Cu-CuO, which rapidly relays electrons and acts as a better catalyst. In this ternary composite, highly active in situ generated Cu(0) is proved to be responsible for the hydride transfer reaction. The mechanism of 4-nitrophenol reduction has been established from supporting TEM studies. To further support our proposition, we have prepared a compositionally similar Cu2O-Cu-CuO nanocomposite using Cu2O and sodium borohydride which however displayed lower rate of reduction than that of the in situ produced ternary nanocomposite. The evolution of isolated Cu(0) nanoparticles for 4-nitrophenol reduction from Cu2O under surfactant-free condition has also been taken into consideration. The synthetic procedures of cuprous oxide as well as its catalytic activity in the reduction of 4-nitrophenol are very convenient, fast, cost-effective, and easily operable in aqueous medium and were followed spectrophotometrically. Additionally, the Cu2O-catalyzed 4-nitrophenol reduction methodology was extended further to the reduction of electronically diverse nitroarenes. This concise catalytic process in aqueous medium at room temperature revealed an unprecedented catalytic performance which would draw attention across the whole research community.
Sasmal, Anup Kumar,Dutta, Soumen,Pal, Tarasankar
p. 3139 - 3150
(2016)
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Development of a continuous-flow system for catalysis with palladium(0) particles
Heterogeneous catalysis for organic synthesis under continuous-flow conditions becomes possible by a new reactor-based approach. Continuous-flow reactors with a monolithic glass/polymer composite interior are loaded with palladium particles by ion exchange followed by reduction. When incorporated into a continuous-flow setup (PASSflow) this reactor allows the transfer-hydrogenation of alkenes, alkynes, nitro-substituted aromatic compounds and benzyl ethers in the flow-through mode. In addition, the activity of the catalysts is well suited to achieve Suzuki, Sonogashira and Heck cross-coupling reactions in the absence of phosphanes or any other ligands, resulting in a greatly simplified purification. As an extension to this concept a bifunctional support was prepared inside the reactor consisting of Pd particles and an ion-exchange group (hydroxide form). In the Suzuki-Miyaura reaction the reactor serves as a base for immobilisation and activation of the boronic acid as boronate and as a catalyst for promoting the C-C coupling reaction under continuous-flow conditions. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.
Solodenko, Wladimir,Wen, Hongliang,Leue, Stefanie,Stuhlmann, Friedrich,Sourkouni-Argirusi, Georgia,Jas, Gerhard,Schoenfeld, Hagen,Kunz, Ulrich,Kirschning, Andreas
p. 3601 - 3610
(2004)
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Chemoselective reduction of nitroaromatics to anilines using decaborane in methanol
Nitrobenzenes were chemoselectively reduced to the corresponding anilines using decaborane (B10H14) in the presence of Pd/C and two drops of acetic acid at reflux under nitrogen atmosphere in high yields.
Bae, Jong Woo,Cho, Young Jin,Lee, Seung Hwan,Yoon, Cheol Min
p. 175 - 177
(2000)
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Efficient reductions of nitroarenes with SnCl2 in ionic liquid
Mild, eco-friendly and fast reductions of nitroarenes to aminoarenes have been accomplished using stannous chloride dihydrate in ionic liquid tetrabutylammonium bromide (TBAB) that provides unsolvated nucleophilic bromide ion. Improved yields, lower reaction time, generality, and a less demanding work-up procedure are the notable features of this protocol.
De, Prithwiraj
p. 1835 - 1837
(2004)
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Reduction of nitro-aryl compounds with zinc in the presence of poly[N-(2-aminoethyl)acrylamido]-trimethylammonium chloride as a phase-transfer catalyst
The new polymeric phase-transfer catalyst, poly[N-(2-aminoethyl)acrylamido] trimethylammonium chloride resin, catalyzes the reduction of nitroarenes to the corresponding aromatic amines with zinc powder in water and in high yields under mild conditions. Copyright Taylor & Francis, Inc.
Mahdavi, Hossen,Tamami, Bahman
p. 1121 - 1127
(2005)
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Thiazole ring-containing amide compounds as well as preparation method and application thereof
The invention discloses thiazole ring-containing amide compounds as well as a preparation method and application thereof, and belongs to the field of chemical technologies and pesticides. According to the present invention, p-phenylenediamine is adopted as a raw material to synthesize a series of the thiazole ring-containing amide compounds, and the synthesized thiazole ring-containing amide compounds have good inhibition effects on Xanthomonas oryzae pv.Oryza (Xoo), Xanthomonas oryzae pv.Oryzcola (Xoc) and Xanthomonas axonophora pv.Citri (Xac) in agricultural diseases and insect pests, and can be used for preparing the anti-plant bacterium agent.
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(2021/06/23)

Selective Carbon-Carbon Bond Amination with Redox-Active Aminating Reagents: A Direct Approach to Anilines?
Amines are among the most fundamental motifs in chemical synthesis, and the introduction of amine building blocks via selective C—C bond cleavage allows the construction of nitrogen compounds from simple hydrocarbons through direct skeleton modification. Herein, we report a novel method for the preparation of anilines from alkylarenes via Schmidt-type rearrangement using redox-active amination reagents, which are easily prepared from hydroxylamine. Primary amines and secondary amines were prepared from corresponding alkylarenes or benzyl alcohols under mild conditions. Good compatibility and valuable applications of the transformation were also displayed.
Qiu, Xu,Wang, Yachong,Su, Lingyu,Jin, Rui,Song, Song,Qin, Qixue,Li, Junhua,Zong, Baoning,Jiao, Ning
supporting information
p. 3011 - 3016
(2021/09/13)

Synthesis of ring-opened derivatives of triazole-containing quinolinones and their antidepressant and anticonvulsant activities
Based on the potent antidepressant and anticonvulsant activities of the triazole-containing quinolinones reported in our previous work, a series of ring-opened derivatives of them were designed, synthesized in this work. Their antidepressant and anticonvulsant activities were screened using the forced swimming test (FST) and the maximal electroshock seizure test (MES), respectively. The results showed that compounds 4a, 5a, 6c-6e, 6g-6i, and 7 led to significant reductions in the accumulated immobility time in the FST at a dose of 50 mg/kg. Especially compound 7 exhibited higher levels of efficacy than the reference standard fluoxetine in the FST and the tail suspension test. The results of an open field test excluded the possibility of central nervous stimulation of 7, which further confirmed its antidepressant effect. Meanwhile, compounds 6a-6i and 7 showed different degrees of anticonvulsant activity in mice at the doses range from 300 to 30 mg/kg in the MES. Among them, compounds 6e and 7 displayed the ED50 of 38.5 and 32.7 mg/kg in the MES, and TD50 of 254.6 and 245.5 mg/kg, respectively. No one showed neurotoxicity at the dose of 100 mg/kg. The preliminary investigation forward to their mechanism indicated that regulation of GABAergic system might contribute to their anticonvulsive and anti-depressive action.
Song, Ming-Xia,Huang, Yu-Shan,Zhou, Qiu-Gui,Deng, Xian-Qing,Yao, Xiao-Dong
(2020/12/07)

Efficient nitriding reagent and application thereof
The invention discloses an efficient nitriding reagent and application thereof, wherein the nitriding reagent comprises nitrogen oxide, an active agent, a reducing agent and an organic solvent. By applying the nitriding reagent, nitrogen-containing compounds such as amide, nitrile and the like can be produced, and the method is simple in condition, low in waste discharge amount and simple in reaction equipment.
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Paragraph 0134-0136

(2021/03/31)

Preparation method of aminoacetanilide
The invention belongs to the technical field of dye intermediate production, and particularly relates to a preparation method of aminoacetanilide, which comprises the following steps of 1) adding an acetate compound, phenylenediamine and a catalyst triethylene diamine into a reactor, and uniformly mixing to obtain a mixed solution, 2) under the protection of nitrogen, heating the mixed solution to65-90 DEG C, dropwise adding acetic acid, and reacting for 4-9 hours after dropwise adding is finished, and 3) after the reaction is finished, cooling to 15-25 DEG C, standing for 5-8 hours, filtering, fully washing a filter cake with n-butyl alcohol, and drying in vacuum at 80 DEG C for 6 hours to obtain aminoacetanilide. Aminoacetanilide is synthesized by using an acetate method, acetic anhydride which is high in price and easy to prepare drugs is not used, the production cost is reduced, and the method is suitable for industrial production; the method has the advantages of few reaction steps, no generation of waste acid, waste water and waste salt and no pollution to the environment; the yield (based on the weight of phenylenediamine) of the aminoacetanilide product prepared by the method is up to 97% or above, and the purity is up to 98% or above.
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Paragraph 0028-0045

(2021/01/29)

Porous polymeric ligand promoted copper-catalyzed C-N coupling of (hetero)aryl chlorides under visible-light irradiation
A porous polymeric ligand (PPL) has been synthesized and complexed with copper to generate a heterogeneous catalyst (Cu@PPL) that has facilitated the efficient C-N coupling with various (hetero)aryl chlorides under mild conditions of visible-light irradiation at 80 °C (58 examples, up to 99% yields). This method could be applied to both aqueous ammonia and substituted amines, and is compatible to a variety of functional groups and heterocycles, as well as allows tandem C-N couplings with conjunctive dihalides. Furthermore, the heterogeneous characteristic of Cu@PPL has enabled a straightforward catalyst separation in multiple times of recycling with negligible catalytic efficiency loss by simple filtration, affording reaction mixtures containing less than 1 ppm of Cu residue. [Figure not available: see fulltext.]
Wang, Erfei,Chen, Kaixuan,Chen, Yinan,Zhang, Jiawei,Lin, Xinrong,Chen, Mao
p. 17 - 21
(2020/11/04)

Synthesis of Substituted Anilines from Cyclohexanones Using Pd/C-Ethylene System and Its Application to Indole Synthesis
The synthesis of anilines and indoles from cyclohexanones using a Pd/C-ethylene system is reported. A simple combination of NH4OAc and K2CO3 under nonaerobic conditions was found to be the most suitable to perform this reaction. Hydrogen transfer between cyclohexanone and ethylene generates the desired products. The reaction tolerates a variety of substitutions on the starting cyclohexanones.
Maeda, Katsumi,Matsubara, Ryosuke,Hayashi, Masahiko
supporting information
p. 1530 - 1534
(2021/03/08)

Selective primary aniline synthesis through supported Pd-catalyzed acceptorless dehydrogenative aromatization by utilizing hydrazine
By utilizing hydrazine (N2H4) as the nitrogen source in the presence of a hydroxyapatite-supported Pd nanoparticle catalyst (Pd/HAP), various primary anilines can be selectively synthesized from cyclohexanonesviaacceptorless dehydrogenative aromatization. The strong nucleophilicity of N2H4and the stability of the hydrazone intermediates can effectively suppress the formation of the undesired secondary aniline byproducts.
Lin, Wei-Chen,Yamaguchi, Kazuya,Yatabe, Takafumi
supporting information
p. 6530 - 6533
(2021/07/07)

Ligand compound for copper catalyzed aryl halide coupling reaction, catalytic system and coupling reaction
The invention provides a ligand compound capable of being used for copper catalyzed aryl halide coupling reaction, the ligand compound is a three-class compound containing a 2-(substituted or non-substituted) aminopyridine nitrogen-oxygen group, and the invention also provides a catalytic system for the aryl halide coupling reaction. Thecatalytic system comprises a copper catalyst, a compound containing a 2-(substituted or non-substituted) aminopyridine nitrogen-oxygen group adopted as a ligand, alkali and a solvent, and meanwhile, the invention also provides a system for the aryl halide coupling reaction adopting the catalyst system. The compound containing the 2-(substituted or non-substituted) aminopyridine nitrogen oxygen group can be used as the ligand for the copper catalyzed aryl chloride coupling reaction, and the ligand is stable under a strong alkaline condition and can well maintain catalytic activity when being used for the copper-catalyzed aryl chloride coupling reaction. In addition, the copper catalyst adopting the compound as the ligand can particularly effectively promote coupling of copper catalyzed aryl chloride and various nucleophilic reagents which are difficult to generate under conventional conditions, C-N, C-O and C-S bonds are generated, and numerous useful small molecule compounds are synthesized. Therefore, the aryl halide coupling reaction has a very good large-scale application prospect by adopting the copper catalysis system of the ligand.
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Paragraph 0111-0119

(2021/05/29)

Copper nanoparticles (CuNPs) catalyzed chemoselective reduction of nitroarenes in aqueous medium
Abstract: A procedure for practical synthesis of CuNPs from CuSO4·5H2O is established, under appropriate reaction conditions, using rice (Oryza sativa) as an economic source of reducing as well as a stabilizing agent. Optical and microscopic techniques are employed for the characterization of the synthesized CuNPs and the sizes of the particles were found to be in the range of 8 ± 2 nm. The nanoparticles are used as a catalyst for chemoselective reduction of aromatic nitro compounds to corresponding amines under ambient conditions and water as a reaction medium. Graphic abstract: CuNPs are synthesized using hydrolysed rice and used as catalyst for chemoselective reduction of nitroarenes to their corresponding amines in water. [Figure not available: see fulltext.]
Chand, Dillip Kumar,Rai, Randhir
(2021/08/20)

Chemoselective reduction of nitroarenes, N-acetylation of arylamines, and one-pot reductive acetylation of nitroarenes using carbon-supported palladium catalytic system in water
Developing and/or modifying fundamental chemical reactions using chemical industry-favorite heterogeneous recoverable catalytic systems in the water solvent is very important. In this paper, we developed convenient, green, and efficient approaches for the chemoselective reduction of nitroarenes, N-acetylation of arylamines, and one-pot reductive acetylation of nitroarenes in the presence of the recoverable heterogeneous carbon-supported palladium (Pd/C) catalytic system in water. The utilize of the simple, effective, and recoverable catalyst and also using of water as an entirely green solvent along with relatively short reaction times and good-to-excellent yields of the desired products are some of the noticeable features of the presented synthetic protocols. Graphic abstract: [Figure not available: see fulltext.].
Zeynizadeh, Behzad,Mohammad Aminzadeh, Farkhondeh,Mousavi, Hossein
p. 3289 - 3312
(2021/05/11)

A Concise Route to Cyclic Amines from Nitroarenes and Ketoacids under Iron-Catalyzed Hydrosilylation Conditions
Starting from nitroarenes, under hydrosilylation conditions, using a well-defined N-heterocyclic carbene iron(0) catalyst, (IMes)Fe(CO)4, the corresponding aniline derivatives were produced in 61–92% isolated yields. More impressively, a selective synthesis of cyclic amines such as pyrrolidines, piperidines and azepanes were conducted from levulinic acid, 1,5- and 1,6-keto acids, respectively. The sequential procedure proceeded under both visible light irradiation and thermal conditions with 20 examples in isolated yields up to 69%. (Figure presented.).
Ammaiyappan, Yuvaraj,Darcel, Christophe,Tongdee, Satawat,Wu, Jiajun
p. 3859 - 3865
(2021/07/12)

A mild and selective Cu(II) salts-catalyzed reduction of nitro, azo, azoxy, N-aryl hydroxylamine, nitroso, acid halide, ester, and azide compounds using hydrogen surrogacy of sodium borohydride
The first mild, in situ, single-pot, high-yielding well-screened copper (II) salt-based catalyst system utilizing the hydrogen surrogacy of sodium borohydride for selective hydrogenation of a broad range of nitro substrates into the corresponding amine under habitancy of water or methanol like green solvents have been described. Moreover, this catalytic system can also activate various functional groups for hydride reduction within prompted time, with low catalyst-loading, without any requirement of high pressure or molecular hydrogen supply. Notably, this system explores a great potential to substitute expensive traditional hydrogenation methodologies and thus offers a greener and simple hydrogenative strategy in the field of organic synthesis.
Kalola, Anirudhdha G.,Prasad, Pratibha,Mokariya, Jaydeep A.,Patel, Manish P.
supporting information
p. 3565 - 3589
(2021/10/12)

Synthesis and Antibacterial Evaluation of N-phenylacetamide Derivatives Containing 4-Arylthiazole Moieties
A series of new N-phenylacetamide derivatives containing 4-arylthiazole moieties was designed and synthesized by introducing the thiazole moiety into the amide scaffold. The structures of the target compounds were confirmed by 1H-NMR, 13C-NMR and HRMS. Their in vitro antibacterial activities were evaluated against three kinds of bacteria-Xanthomonas oryzae pv. Oryzae (Xoo), Xanthomonas axonopodis pv. Citri (Xac) and X.oryzae pv. oryzicola (Xoc)-showing promising results. The minimum 50% effective concentration (EC50) value of N-(4-((4-(4-fluoro-phenyl)thiazol-2-yl)amino)phenyl)acetamide (A1) is 156.7 μM, which is superior to bismerthiazol (230.5 μM) and thiodiazole copper (545.2 μM). A scanning electron microscopy (SEM) investigation has confirmed that compound A1 could cause cell membrane rupture of Xoo. In addition, the nematicidal activity of the compounds against Meloidogyne incognita (M. incognita) was also tested, and compound A23 displayed excellent nematicidal activity, with mortality of 100% and 53.2% at 500 μg/mL and 100 μg/mL after 24 h of treatment, respectively. The preliminary structure-activity relationship (SAR) studies of these compounds are also briefly described. These results demonstrated that phenylacetamide derivatives may be considered as potential leads in the design of antibacterial agents.
Jin, Linhong,Lu, Hui,Wang, Lei,Zhou, Xia
(2020/04/23)

Nitromethane as a nitrogen donor in Schmidt-type formation of amides and nitriles
The Schmidt reaction has been an efficient and widely used synthetic approach to amides and nitriles since its discovery in 1923. However, its application often entails the use of volatile, potentially explosive, and highly toxic azide reagents. Here, we report a sequence whereby triflic anhydride and formic and acetic acids activate the bulk chemical nitromethane to serve as a nitrogen donor in place of azides in Schmidt-like reactions. This protocol further expands the substrate scope to alkynes and simple alkyl benzenes for the preparation of amides and nitriles.
Jiao, Ning,Liu, Jianzhong,Qiu, Xu,Song, Song,Wei, Jialiang,Wen, Xiaojin,Zhang, Cheng,Zhang, Ziyao
supporting information
p. 281 - 285
(2020/01/28)

An Electrochemical Beckmann Rearrangement: Traditional Reaction via Modern Radical Mechanism
Abstract: Electrosynthesis as a potential means of introducing heteroatoms into the carbon framework is rarely studied. Herein, the electrochemical Beckmann rearrangement, i. e. the direct electrolysis of ketoximes to amides, is presented for the first time. Using a constant current as the driving force, the reaction can be easily carried out under neutral conditions at room temperature. Based on a series of mechanistic studies, a novel radical Beckmann rearrangement mechanism is proposed. This electrochemical Beckmann rearrangement does not follow the trans-migration rule of the classical Beckmann rearrangement.
Tang, Li,Wang, Zhi-Lv,He, Yan-Hong,Guan, Zhi
p. 4929 - 4936
(2020/08/21)

C-H Amination of Arenes with Hydroxylamine
This Letter describes the development of a TiIII-mediated reaction for the C-H amination of arenes with hydroxylamine. This reaction is applied to a variety of electron-rich (hetero)arene substrates, including a series of natural products and pharmaceuticals. It offers the advantages of mild conditions (room temperature), fast reaction rates (30 min), compatibility with ambient moisture and air, scalability, and the use of inexpensive commercial reagents.
See, Yi Yang,Sanford, Melanie S.
p. 2931 - 2934
(2020/04/09)

Visible Light-Induced Amide Bond Formation
A metal-, base-, and additive-free amide bond formation reaction was developed under an organic photoredox catalyst. This green approach showed excellent functional selectivity without affecting other functional groups such as alcohols, phenols, ethers, esters, halogens, or heterocycles. This method featured a broad substrate scope, good compatibility with water and air, and high yields (≤95%). The potential utilities were demonstrated by the synthesis of important drug molecules such as paracetamol, melatonin, moclobemide, and acetazolamide.
Song, Wangze,Dong, Kun,Li, Ming
supporting information
p. 371 - 375
(2019/11/29)

Method for preparing amide by visible light-induced metal-free participation (by machine translation)
The method for preparing the amide in the, preparation method of the novel amide disclosed by the invention has the advantages that, the reaction: conditions are mild, the 9 - reaction conditions are mild, and the yield 71%. of the reaction conditions is not lower than the reaction conditions . (by machine translation)
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Paragraph 0063-0066

(2020/02/14)

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)

Radical arylation of triphenyl phosphite catalyzed by salicylic acid: Mechanistic investigations and synthetic applications
A straightforward and scalable methodology to synthesize diphenyl arylphosphonates at 20 °C within 1-2 h is reported using inexpensive SA as the catalytic promoter of the reaction. Mechanistic investigations suggest that the reaction proceeds via radical-radical coupling, consistent with the so-called persistent radical effect. The reaction tolerated a wide range of functional groups and heteroaromatic moieties. The synthetic usefulness and the unique reactivity of the obtained phosphonates were demonstrated in different one-step transformations.
Estruch-Blasco, Manel,Felipe-Blanco, Diego,Bosque, Irene,Gonzalez-Gomez, Jose C.
p. 14473 - 14485
(2020/12/29)

From alkylarenes to anilines via site-directed carbon–carbon amination
Anilines are fundamental motifs in various chemical contexts, and are widely used in the industrial production of fine chemicals, polymers, agrochemicals and pharmaceuticals. A recent development for the synthesis of anilines uses the primary amination of C–H bonds in electron-rich arenes. However, there are limitations to this strategy: the amination of electron-deficient arenes remains a challenging task and the amination of electron-rich arenes has a limited control over regioselectivity—the formation of meta-aminated products is especially difficult. Here we report a site-directed C–C bond primary amination of simple and readily available alkylarenes or benzyl alcohols for the direct and efficient preparation of anilines. This chemistry involves a novel C–C bond transformation and offers a versatile protocol for the synthesis of substituted anilines. The use of O2 as an environmentally benign oxidant is demonstrated, and studies on model compounds suggest that this method may also be used for the depolymerization of lignin.
Liu, Jianzhong,Qiu, Xu,Huang, Xiaoqiang,Luo, Xiao,Zhang, Cheng,Wei, Jialiang,Pan, Jun,Liang, Yujie,Zhu, Yuchao,Qin, Qixue,Song, Song,Jiao, Ning
p. 71 - 77
(2018/11/10)

Aromatic amine compound synthesis method
The invention discloses an aromatic amine compound synthesis method which is characterized in that the method is implemented according to any of two methods. The first method includes the steps: mixing an alkyl aromatic compound with a general formula (I) and a nitrogen-containing compound with a general formula (II); performing reaction on mixture under an oxidizing agent and an organic solvent to obtain an aromatic amine compound with a general formula (III). The second method includes the steps: mixing an aromatic alcohol derivative with a general formula (I') and the nitrogen-containing compound with the general formula (II); performing reaction on mixture under an acid additive and an organic solvent to prepare the aromatic amine compound with the general formula (III). According to the method, a lot of alkyl aromatic compounds or aromatic alcohol derivatives firstly serve as raw materials, and the raw materials are reacted to generate the aromatic amine compound without the action of metal catalysis. Compared with a traditional synthesis method, the synthesis method has the advantages that the method is high in yield and simple in condition, waste discharging amount is less,metal participation is omitted, a reaction device is simple, industrial production is easily achieved and the like. The method has a wide application prospect.
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Paragraph 0117-0119

(2019/01/23)

Probing 2H-Indazoles as Templates for SGK1, Tie2, and SRC Kinase Inhibitors
The broader and systematic application of a novel scaffold is often hampered by the unavailability of a short and reliable synthetic access. We investigated a new strategy for the design and synthesis of an array of N2-substituted aza-2H-indazole derivatives as potential kinase inhibitors. Guided by a rational ligand alignment approach to qualify the so-far underrepresented aza-2H-indazole scaffold, indazoles were connected at the N2 position with a phenyl spacer and an arylsulfonamide or amide linkage. Initial profiling against a panel of 30 kinases confirmed the in silico predicted selectivity bias. A synthesized focused library of 52 different aza-2H-indazole derivatives showed good initial selective inhibition against SGK1, Tie2, and SRC kinases, with the best representatives having IC50 values in the range of 500 nm. In a comparative computational study, these data were analyzed and rationalized in light of docking studies.
Schoene, Jens,Gazzi, Thais,Lindemann, Peter,Christmann, Mathias,Volkamer, Andrea,Nazaré, Marc
p. 1514 - 1527
(2019/08/07)

Selective Synthesis of Primary Anilines from NH3 and Cyclohexanones by Utilizing Preferential Adsorption of Styrene on the Pd Nanoparticle Surface
Dehydrogenative aromatization is one of the attractive alternative methods for directly synthesizing primary anilines from NH3 and cyclohexanones. However, the selective synthesis of primary anilines is quite difficult because the desired primary aniline products and the cyclohexanone substrates readily undergo condensation affording the corresponding imines (i.e., N-cyclohexylidene-anilines), followed by hydrogenation to produce N-cyclohexylanilines as the major products. In this study, primary anilines were selectively synthesized in the presence of supported Pd nanoparticle catalysts (e.g., Pd/HAP, HAP=hydroxyapatite, Ca10(PO4)6(OH)2) by utilizing competitive adsorption unique to heterogeneous catalysis; in other words, when styrene was used as a hydrogen acceptor, which preferentially adsorbs on the Pd nanoparticle surface in the presence of N-cyclohexylidene-anilines, various structurally diverse primary anilines were selectively synthesized from readily accessible NH3 and cyclohexanones. The Pd/HAP catalyst was reused several times though its catalytic performance gradually declined.
Koizumi, Yu,Jin, Xiongjie,Yatabe, Takafumi,Miyazaki, Ray,Hasegawa, Jun-ya,Nozaki, Kyoko,Mizuno, Noritaka,Yamaguchi, Kazuya
supporting information
p. 10893 - 10897
(2019/07/12)

SO2F2-Activated Efficient Beckmann Rearrangement of Ketoximes for Accessing Amides and Lactams
A novel, mild and practical protocol for the efficient activation of the Beckmann rearrangement utilizing the readily available and economical sulfuryl fluoride (SO2F2 gas) has been developed. The substrate scope of the operationally simple methodology has been demonstrated by 37 examples with good to nearly quantitative isolated yields (over 90 % yield in most cases) in a short time, including B(OH)2, COOH, NH2, and OH substituted substrates. A tentative mechanism was proposed involving formation and elimination of key intermediate, sulfonyl ester.
Zhang, Guofu,Zhao, Yiyong,Xuan, Lidi,Ding, Chengrong
supporting information
p. 4911 - 4915
(2019/07/31)

Method for preparing aromatic amine compounds from aromatic nitro compounds by catalytic reduction of nano porous gold catalyst
The invention discloses a method for preparing aromatic amine compounds from aromatic nitro compounds by catalytic reduction of a nano porous gold catalyst. The nano porous gold catalyst and the aromatic nitro compounds are taken as substrates and subjected to a reaction in methanol with ammonia borane as a hydrogen source at the room temperature, and a product is obtained. The high probability ofagglomeration of conventional granular catalysts is prevented, the nano porous gold catalyst shows excellent structural stability and good recycling efficiency, has excellent universality, especiallyfor the aromatic nitro compounds, and has green and mild catalytic conditions, high yield and good selectivity. The yield of m-nitroaniline from m-nitrotoluene can reach 98%. Moreover, the catalyst can be centrifugally recovered and can be recycled without other treatment, the yield of preparing m-nitroaniline from m-nitrotoluene by catalyzing can still reach 88% after being recycled five times,and thus, waste is effectively avoided. The catalyst shows high activity during the reaction and excellent stability under the reaction conditions.
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Paragraph 0024; 0025

(2019/07/04)

COMPOSITION FOR PREVENTING OR TREATING HAIR LOSS INCLUDING BENZENE DIAMINE DERIVATIVE
Provided are a compound represented by the following Formula I, or a solvate, stereoisomer, or pharmaceutically acceptable salt thereof, and a composition for preventing or treating hair loss, the compound including the compound as an active ingredient:
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Paragraph 0057; 0070-0071

(2019/04/14)

Green and convenient protocols for the efficient reduction of nitriles and nitro compounds to corresponding amines with NaBH4 in water catalyzed by magnetically retrievable CuFe2O4 nanoparticles
Abstract: In this study, firstly, CuFe2O4 nanoparticles were prepared by a simple operation. The structure of the mentioned nanoparticles was characterized by Fourier transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy, transmission electron microscopy, energy-dispersive X-ray spectroscopy, inductively coupled plasma-optical emission spectrometry, vibrating sample magnetometer and also Brunauer–Emmett–Teller and Barrett–Joyner–Halenda analyses. The prepared magnetically copper ferrite nanocomposite was successfully applied as a simple, cost-effective, practicable, and recoverable catalyst on the green, highly efficient, fast, base-free, and ligand-free reduction of nitriles and also on the affordable and eco-friendly reduction of nitro compounds with the broad substrate scope to the corresponding amines with NaBH4 in water at reflux in high to excellent yields. Graphical abstract: [Figure not available: see fulltext.].
Zeynizadeh, Behzad,Mohammad Aminzadeh, Farkhondeh,Mousavi, Hossein
(2019/03/23)

Synergistic Effects of ppm Levels of Palladium on Natural Clinochlore for Reduction of Nitroarenes
Augmenting the modified naturally occurring clay clinochlore with ppm amounts of palladium leads to a new and very effective reagent for the reduction of numerous aromatic nitro species. When palladium nanoparticles are supported on pyridyltriazole-modified clinochlore, iron within clinochlore acts synergistically with palladium to catalyze the reduction of a wide variety of nitroarenes at room temperature in aqueous media. Based on E-factor calculations, the catalyst system is found to be in line with green chemistry standards and can be recycled up to five times.
Gholinejad, Mohammad,Oftadeh, Erfan,Shojafar, Mohammad,Sansano, José M.,Lipshutz, Bruce H.
p. 4240 - 4248
(2019/09/06)

Simple Nickel Salts for the Amination of (Hetero)aryl Bromides and Iodides with Lithium Bis(trimethylsilyl)amide
Recent developments in the chemistry of C-N bond formation and the synthesis of anilines have allowed for the use of first-row transition metals to catalyze these transformations. Much of the progress in this area has been driven by comprehensive screening for privileged/tailored ligands, which can be costly and not readily available in a research laboratory setting. In this communication we report a protocol in which simple nickel salts catalyze the C-N cross-coupling reaction between (hetero)aryl bromides and iodides with lithium bis(trimethylsilyl)amide without the need for any additive ligand. This method is amenable to low nickel catalyst loadings (1%) as well as gram-scale reactions. Because of the good functional group tolerance and compatibility with heterocyclic moieties, this method is useful for academic laboratory settings where access to tailored ligands and noble-metal catalysts could be challenging.
Martinez, Gabriel Espinosa,Nugent, Joseph W.,Fout, Alison R.
supporting information
p. 2941 - 2944
(2018/09/21)

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)

Mild, calcium catalysed Beckmann rearrangements
A mild calcium catalysed Beckmann rearrangement has been realised, which forgoes the more traditional harsh reactions conditions associated with the transformation. The catalyst system is shown to be tolerant towards a wide variety of functional groups relevant to natural product synthesis and medicinal chemistry and the synthetic utility of the reaction has also been investigated. A preliminary mechanistic investigation was performed to understand the nature of the incoming nucleophile and a possible reaction pathway is described.
Kiely-Collins,Sechi,Brennan,McLaughlin
supporting information
p. 654 - 657
(2018/02/06)

Simple and Practical Synthesis of Various New Nickel Boride-Based Nanocomposites and their Applications for the Green and Expeditious Reduction of Nitroarenes to Arylamines under Wet-Solvent-Free Mechanochemical Grinding
In this paper, we report a simple synthesis of four new nickel boride-based nanocomposites, namely Ni2B@ZrCl4, Ni2B@Cu2O, Ni2B@CuCl2 and Ni2B@FeCl3, from commercially available and cheap starting materials. All of the new Ni2B-based nanocomposites were well characterized by Fourier-transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy, and energy-dispersive X-ray spectroscopy. Further, the catalytic applications of these new nanocomposites were successfully evaluated in the wet-solvent-free reduction of aromatic nitro compounds to arylamines with sodium borohydride (NaBH4) at room temperature by a mechanochemical grinding technique. All the introduced catalytic systems provide excellent yields of arylamines in very short reaction times for a wide range of substrates. Also, recoverability and reusability of the new nanocomposites were investigated.
Mousavi, Hossein,Zeynizadeh, Behzad,Younesi, Reza,Esmati, Mozhgan
p. 595 - 609
(2018/09/10)

BENZOTHIADIAZINE COMPOUNDS
The invention is directed to substituted benzothiadiazine derivatives. Specifically, the invention is directed to compounds according to Formula (I):wherein R, R1, R2, R3, R4 and R5 are as defined herein. The compounds of the invention are inhibitors of CD73 and can be useful in the treatment of cancer, pre-cancerous syndromes and diseases associated with CD73 inhibition, such as AIDS, autoimmune diseases, infections, atherosclerosis, and ischemia-reperfusion injury. Accordingly, the invention is further directed to pharmaceutical compositions comprising a compound of the invention. The invention is still further directed to methods of inhibiting CD73 activity and treatment of disorders associated therewith using a compound of the invention or a pharmaceutical composition comprising a compound of the invention.
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(2017/07/23)

Fe-Catalyzed Amination of (Hetero)Arenes with a Redox-Active Aminating Reagent under Mild Conditions
A novel and efficient Fe-catalyzed direct C?H amination (NH2) of arenes is reported using a new redox-active aminating reagent. The reaction is simple, and can be performed under air, mild, and redox-neutral conditions. This protocol has a broad substrate scope and could be used in the late-stage modification of bioactive compounds. Mechanistic studies demonstrate that a radical pathway could be involved in this transformation.
Liu, Jianzhong,Wu, Kai,Shen, Tao,Liang, Yujie,Zou, Miancheng,Zhu, Yuchao,Li, Xinwei,Li, Xinyao,Jiao, Ning
supporting information
p. 563 - 567
(2017/01/18)

Rapid and convenient conversion of nitroarenes to anilines under microwave conditions using nonprecious metals in mildly acidic medium
Nitroarenes are reduced to the corresponding aniline derivatives using iron or zinc under mild conditions under microwave heating conditions. Mild acidity is provided by ammonium chloride in an aqueous methanol medium. The conditions are tolerant to other functional groups, with the exception of bromoalkyl derivatives, which yield complex reaction mixtures; otherwise, yields are generally quite high (80–99%).
Keenan, Corey S.,Murphree, S. Shaun
supporting information
p. 1085 - 1089
(2017/05/25)

PVP-Pd nanoparticles as efficient catalyst for nitroarene reduction under mild conditions in aqueous media
The catalytic activity of PVP-Pd nanoparticles synthesized by electrochemical methods was explored in nitroaromatic hydrogenation reaction. In this transformation, the colloidal nanocatalyst proved to have outstanding catalytic activity under sustainable reaction conditions. This mild process efficiently reduced the nitroaromatic group at room temperature, without high pressure of molecular hydrogen and in aqueous medium. Furthermore, several functional groups were tolerated, given the corresponding substituted arylamines in excellent yields and with high TOF. In addition, one-pot reactions and tandem process were explored, in which nitroaromatic hydrogenation reaction was included in the synthesis of modified amines. This methodology was effectively incorporated in tandem reactions and one-pot procedures, achieving N-arylamines functionalized in good isolated yields. Finally, comparison of sustainable chemistry metrics analysis demonstrated that this methodology is a reliable approach to perform the nitro compound hydrogenation process.
Uberman, Paula M.,García, Carolina S.,Rodríguez, Julieta R.,Martín, Sandra E.
supporting information
p. 739 - 748
(2017/05/19)

Catalytic Materials Based on Surface Coating with Poly(ethyleneimine)-Stabilized Gold Nanoparticles
Gold nanoparticles (AuNPs) can be obtained from HAuCl4 by using poly(ethyleneimine) (PEI) as both reductant and stabilizing agent. However, the known affinity of PEI for different materials has not been exploited to coat them and turn their surface catalytic. We demonstrate that the irradiation of a solution of HAuCl4 and branched PEI 1800 (bPEI2K) with microwave (MW) yields PEI-stabilized AuNPs (MW-PEI@AuNPs) with an average size of 7.6 nm that are catalytically active in the reduction with NaBH4 of different nitroarenes functionalized with a variety of functional groups. Moreover, the as-prepared MW-PE@-AuNPs show affinity for different materials such as polystyrene (standard spectrophotometry disposal cuvettes), polypropylene (Falcon-type tubes), and silica (Silica gel 60), turning their surface catalytic without any additional synthetic step. This feature was exploited to transform standard tubing (Tygon, poly(ether ether ketone), and stainless steel) into flow reactors by simple passage of a solution of MW-PEI@AuNPs. This straightforward functionalization is especially appealing in the case of the stainless-steel tubing, one of the materials more widely used in HPLC, which is of interest for flow nanocatalysis.
Ortega-Mu?oz, Mariano,Blanco, Victor,Hernandez-Mateo, Fernando,Lopez-Jaramillo, F. Javier,Santoyo-Gonzalez, Francisco
p. 3965 - 3973
(2017/09/14)

Direct and practical synthesis of primary anilines through iron-catalyzed C-H bond amination
The direct C-H amination of arenes is an important strategy to streamline the discovery and preparation of functional molecules. Herein, we report an operationally simple arene C-H amination reaction that, in contrast to most literature precedent, affords directly the synthetically versatile primary aniline products without relying on protecting group manipulations. Inexpensive Fe(II)-sulfate serves as a convenient catalyst for the transformation. The reaction tolerates a wide scope of arenes, including structurally complex drugs. Importantly, the arene substrates are used as limiting reagents in the transformation. This operationally simple transformation should considerably accelerate the discovery of medicines and functional molecules.
Legnani, Luca,Cerai, Gabriele Prina,Morandi, Bill
p. 8162 - 8165
(2018/05/22)

HEPARAN SULFATE BIOSYNTHESIS INHIBITORS FOR THE TREATMENT OF DISEASES
Described herein are compounds of Formula I, methods of making such compounds, pharmaceutical compositions and medicaments containing such compounds, and methods of using such compounds to treat or prevent diseases or conditions in need of inhibition of heparan sulfate biosynthesis.
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(2016/05/02)

Discovery and Structure-Based Optimization of 2-Ureidothiophene-3-carboxylic Acids as Dual Bacterial RNA Polymerase and Viral Reverse Transcriptase Inhibitors
We are concerned with the development of novel anti-infectives with dual antibacterial and antiretroviral activities for MRSA/HIV-1 co-infection. To achieve this goal, we exploited for the first time the mechanistic function similarity between the bacterial RNA polymerase (RNAP) "switch region" and the viral non-nucleoside reverse transcriptase inhibitor (NNRTI) binding site. Starting from our previously discovered RNAP inhibitors, we managed to develop potent RT inhibitors effective against several resistant HIV-1 strains with maintained or enhanced RNAP inhibitory properties following a structure-based design approach. A quantitative structure-activity relationship (QSAR) analysis revealed distinct molecular features necessary for RT inhibition. Furthermore, mode of action (MoA) studies revealed that these compounds inhibit RT noncompetitively, through a new mechanism via closing of the RT clamp. In addition, the novel RNAP/RT inhibitors are characterized by a potent antibacterial activity against S. aureus and in cellulo antiretroviral activity against NNRTI-resistant strains. In HeLa and HEK 293 cells, the compounds showed only marginal cytotoxicity.
Elgaher, Walid A. M.,Sharma, Kamal K.,Haupenthal, J?rg,Saladini, Francesco,Pires, Manuel,Real, Eleonore,Mély, Yves,Hartmann, Rolf W.
p. 7212 - 7222
(2016/08/24)

P4VPy–CuO nanoparticles as a novel and reusable catalyst: application at the protection of alcohols, phenols and amines
P4VPy–CuO nanoparticles were synthesized using ultrasound irradiations. Relevant properties of the synthesized nanoparticles were investigated by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and Fourier transform infrared spectroscopy. After identification, the prepared reagent was used for the promotion of different types of protection reactions of alcohols, phenols and amines. Easy workup, short reaction times, excellent yields, relatively low cost and reusability of the catalyst are the striking features of the reported methods.
Shirini, Farhad,Fallah-Shojaei, Abdollah,Abedini, Masoumeh,Samavi, Laleh
p. 1699 - 1712
(2016/07/27)

N-Acyl-N-(4-chlorophenyl)-4-nitrobenzenesulfonamides: Highly selective and efficient reagents for acylation of amines in water
A variety of N-acyl-N-(4-chlorophenyl)-4-nitrobenzenesulfonamides (1a-e) were synthesized in one pot from 4-chloroaniline under solvent-free conditions and have been developed as chemoselective N-acylation reagents. Selective protection of primary amines in the presence of secondary amines, acylation of aliphatic amines in the presence of aryl amines, and monofunctionalization of primary-secondary diamines as well as selective N-acylation of amino alcohols using these reagents are described. All of the acylation reactions were carried out in water as a green solvent. High stability and easy preparation of these acylating reagents are other advantages of this method.
Ebrahimi, Sara,Saiadi, Safoura,Dakhilpour, Simin,Mirsattari, Seyed Nezamoddin,Massah, Ahmad Reza
p. 95 - 104
(2016/04/26)

Fast and efficient protocol for solvent-free reduction of nitro compounds to amines with NaBH4 in the presence of bis-thiourea complexes of bivalent cobalt nickel, copper and zinc chlorides
Reduction of nitro compounds to the corresponding amines has been carried out efficiently with NaBH4 in the presence of bis-thiourea complexes of bivalent cobalt, nickel, copper and zinc chlorides, [MII(tu)2Cl2]. The reactions were carried out under solvent-free conditions at room temperature to afford amines in high to excellent yields. Comparison of the results showed that the reducing capability of NaBH4 was influenced with bis-thiourea complexes as: Co(tu)2Cl2> Ni(tu)2Cl2> Cu(tu)2Cl2> Zn(tu)2Cl2.
Zeynizadeh, Behzad,Sorkhabi, Serve
p. 679 - 684
(2016/10/30)

One-pot synthesis of 1,4-disubstituted 1,2,3-triazoles from nitrobenzenes
A facile synthesis of 1,4-disubstituted 1,2,3-triazoles was achieved from nitrobenzenes and terminal alkynes under mild conditions. The reactions were successful for nitrobenzenes and terminal alkynes bearing various functionalities, from which the 1,2,3-triazole derivatives were smoothly synthesized through a four-step one-pot sequence.
Zhao, Fen,Chen, Zhen,Xie, Kai,Yang, Rui,Jiang, Yu-Bo
p. 109 - 113
(2016/01/25)

An easily accessible and recyclable copper nanoparticle catalyst for the solvent-free synthesis of dipyrromethanes and aromatic amines
A facile method to prepare a reusable copper nanocatalyst is reported. Transmission electron microscopy shows that the CuNPs are spherical in nature and reside in the nanoscopic template of the capping agent, guar gum. Powder X-ray diffraction studies confirm the crystalline nature of the CuNPs. The catalytic efficiency and recyclability of the synthesized CuNPs were demonstrated through the synthesis of dipyrromethanes (DPMs) and aromatic amines. Various DPMs are obtained in very good yields under solvent-free conditions and nitroarenes are converted to the corresponding amino compounds within 10 min, as evidenced by the kinetic study.
Megarajan, Sengan,Ayaz Ahmed, Khan Behlol,Rajmohan, Rajamani,Vairaprakash, Pothiappan,Anbazhagan, Veerappan
p. 103065 - 103071
(2016/11/13)

Synthesis and in-vitro evaluation of 2-amino-4-arylthiazole as inhibitor of 3D polymerase against foot-and-mouth disease (FMD)
Foot-and-mouth disease (FMD) is a highly contagious vesicular disease of livestock caused by a highly variable RNA virus, foot-and-mouth disease virus (FMDV). One of the targets to suppress expansion of and to control FMD is 3D polymerase (FMDV 3Dpol). In this study, 2-amino-4-arylthiazole derivatives were synthesized and evaluated for their inhibitory activity against FMDV 3Dpol. Among them, compound 20i exhibited the most potent functional inhibition (IC50 = 0.39μM) of FMDV 3D polymerase and compound 24a (EC50=13.09 μM) showed more potent antiviral activity than ribavirin (EC50=1367 μM) and T1105 (EC50=347 μM) with IBRS-2 cells infected by the FMDV O/SKR/2010 strain.
Jeong, Kwi-Wan,Lee, Jung-Hun,Park, Sun-Mi,Choi, Joo-Hyung,Jeong, Dae-Youn,Choi, Dong-Hwa,Nam, Yeonju,Park, Jong-Hyeon,Lee, Kwang-Nyeong,Kim, Su-Mi,Ku, Jin-Mo
p. 387 - 397
(2015/09/01)

Pyrrole inhibitors of S-nitrosoglutathione reductase as therapeutic agents
The present invention is directed to inhibitors of S-nitrosoglutathione reductase (GSNOR), pharmaceutical compositions comprising such GSNOR inhibitors, and methods of making and using the same.
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(2015/11/16)