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Phenotyping Reveals Targets of a Pseudo-Natural-Product Autophagy Inhibitor
Pseudo-natural-product (NP) design combines natural product fragments to provide unprecedented NP-inspired compounds not accessible by biosynthesis, but endowed with biological relevance. Since the bioactivity of pseudo-NPs may be unprecedented or unexpected, they are best evaluated in target agnostic cell-based assays monitoring entire cellular programs or complex phenotypes. Here, the Cinchona alkaloid scaffold was merged with the indole ring system to synthesize indocinchona alkaloids by Pd-catalyzed annulation. Exploration of indocinchona alkaloid bioactivities in phenotypic assays revealed a novel class of azaindole-containing autophagy inhibitors, the azaquindoles. Subsequent characterization of the most potent compound, azaquindole-1, in the morphological cell painting assay, guided target identification efforts. In contrast to the parent Cinchona alkaloids, azaquindoles selectively inhibit starvation- and rapamycin-induced autophagy by targeting the lipid kinase VPS34.
Corkery, Dale,Foley, Daniel J.,Laraia, Luca,Pahl, Axel,Waldmann, Herbert,Wu, Yao-Wen,Zinken, Sarah
p. 12470 - 12476
(2020)
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Efficient and recyclable bimetallic Co–Cu catalysts for selective hydrogenation of halogenated nitroarenes
Silica supported N-doped carbon layers encapsulating Co–Cu nanoparticles (Co1Cux@CN/SiO2) were prepared by a one-step impregnation of Co(NO3)2·6H2O, Cu(NO3)2·3H2O, urea and glucose, following in situ carbothermal reduction. Effects of Cu contents on the catalytic performance of the Co1Cux@CN/SiO2 catalysts were investigated for selective hydrogenation of p-chloronitrobenzene to p-chloroaniline. The Co1Cu0.30@CN/SiO2 with Cu/Co molar ratio of 0.30:1 presented much higher activity and stability than the monometallic Co@CN/SiO2 catalyst. The addition of Cu into Co1Cux@CN/SiO2 catalysts had favorable effects on the formation of highly active Co–N sites and N-doped carbon layer. The role of the N-doped carbon layer was to protect the Co from oxidation by air, and the Co1Cu0.30@CN/SiO2 could be reused for at least 12 cycles without decrease in catalytic efficiency. Mechanistic and in situ infrared studies revealed that the interaction effect between the Co and Cu atoms made the surface of Co highly electron rich, which decreased adsorption of halogen groups and resulting in the enhanced selectivity during chemoselective hydrogenation of halogenated nitroarenes for a wide scope of substrates.
Lu, Xionggang,Ren, Jiaan,Sheng, Yao,Wang, Xueguang,Wu, Baoqin,Zou, Xiujing
(2021/12/20)

In situcreation of multi-metallic species inside porous silicate materials with tunable catalytic properties
Porous metal silicate (PMS) material PMS-11, consisting of uniformly distributed multi-metallic species inside the pores, is synthesized by using a discrete multi-metal coordination complex as the template, demonstrating high catalytic activity and selectivity in hydrogenation of halogenated nitrobenzenes by synergistically activating different reactant moleculesviaNi and Co transition metal centers, while GdIIILewis acid sites play a role in tuning the catalytic properties.
Liu, Yang-Yang,Wu, Chuan-De,Zhan, Guo-Peng
supporting information
p. 6185 - 6188
(2021/06/30)

NaI/PPh3-Mediated Photochemical Reduction and Amination of Nitroarenes
A mild transition-metal- and photosensitizer-free photoredox system based on the combination of NaI and PPh3 was found to enable highly selective reduction of nitroarenes. This protocol tolerates a broad range of reducible functional groups such as halogen (Cl, Br, and even I), aldehyde, ketone, carboxyl, and cyano. Moreover, the photoredox catalysis with NaI and stoichiometric PPh3 provides also an alternative entry to Cadogan-type reductive amination when o-nitrobiarenes were used.
Qu, Zhonghua,Chen, Xing,Zhong, Shuai,Deng, Guo-Jun,Huang, Huawen
supporting information
p. 5349 - 5353
(2021/07/21)

Cobalt nanoclusters coated with N-doped carbon for chemoselective nitroarene hydrogenation and tandem reactions in water
The development of active and selective non-noble metal-based catalysts for the chemoselective reduction of nitro compounds in aquo media under mild conditions is an attractive research area. Herein, the synthesis of subnanometric and stable cobalt nanoclusters, covered by N-doped carbon layers as core-shell (Co@NC-800), for the chemoselective reduction of nitroarenes is reported. TheCo@NC-800catalyst was prepared by the pyrolysis of the Co(tpy)2complex impregnated on Vulcan carbon. In fact, the use of a molecular complex based on six N-Co bonds drives the formation of a well-defined and distributed cobalt core-shell nanocluster covered by N-doped carbon layers. In order to elucidate its nature, it has been fully characterized by using several advanced techniques. In addition, this as-prepared catalyst showed high activity, chemoselectivity and stability toward the reduction of nitro compounds with H2and under mild reaction conditions; water was used as a green solvent, improving the previous results based on cobalt catalysts. Moreover, theCo@NC-800catalyst is also active and selective for the one-pot synthesis of secondary aryl amines and isoindolinones through the reductive amination of nitroarenes. Finally, based on diffraction and spectroscopic studies, metallic cobalt nanoclusters with surface CoNxpatches have been proposed as the active phase in theCo@NC-800material.
Agostini, Giovanni,Calvino, Jose. J.,Corma, Avelino,Gutiérrez-Tarri?o, Silvia,Lopes, Christian W.,O?a-Burgos, Pascual,Rojas-Buzo, Sergio
supporting information
p. 4490 - 4501
(2021/06/28)

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)

New indolo[1,2-c]quinazolines for single-crystal field-effect transistor: A united experimental and theoretical studies
Here, we account the synthesis and characterization of a series of symmetrical fused heterocyclic aromatic hydrocarbons (HAHs) with an indolo[1,2-c]quinazoline (IQ) as the core moiety. All the new HAHs IQ series were systematically investigated by using various spectroscopic methods. Furthermore, their photo-physical properties were supported by density functional theory (DFT) and time-dependent density functional theory (TDDFT) studies to support the experimental findings. The tetramethyl-substituted indolo[1,2-c]quinazoline (TMIQ) compound is shown to exhibit the shifted type of π–π stacking interactions, which render this series as a new semiconducting material. Single-crystal-based field-effect transistor devices of TMIQ exhibited efficient charge transport behavior, giving a p-channel field-effect mobility of 0.25 cm2?V?1?s?1 with an on/off ratio of 5 × 105.
Puli, Venkat Swamy,Kilaru, Suresh,Bhongiri, Yadagiri,Marri, Sreenath Reddy,Tripathi, Anuj,Chetti, Prabhakar,Chatterjee, Anindita,Vukoti, Kiran Kumar,Pola, Someshwar
(2021/08/30)

New Indolo[3,2-b]indole based small organic molecules for Organic Thin Film Transistors (OTFTs): A combined experimental and DFT Study
Synthesis of new indolo[3,2-b]indoles (5a- 5j) in presence of Ag-doped ZnO and (Diacetoxyiodo) benzene system under visible-light have been reported. All the new fused linear heterocyclic indolo[3,2-b]indole systems (5a- 5j) thoroughly characterized by spectroscopic methods like mass, UV-visible, NMR and C, H, N elemental analysis. Further, their photophysical properties were carried out by combined experimental and theoretical studies. Thermogravimetric studies are carried out to confirm the thermal stability of molecules. The frontier molecular orbitals of molecules are characterized with the help of cyclic voltammetry. Additionally, the compounds of series 5 were used for the fabrication of organic thin-film transistors, which indicated the hole mobilities in the range of 0.11 – 0.85 cm2/Vs and with on/off ratio 105 on ODTS-SiO2 substrate at 50 °C and are also supported by DFT studies.
Puli, Venkat Swamy,Subburu, Mahesh,Bhongiri, Yadagiri,Tripathi, Anuj,Prasad,Chatterjee, Anindita,Pola, Someshwar,Chetti, Prabhakar
(2020/11/04)

Synthesis of Stannylated Aryl Imines and Amines via Aryne Insertion Reactions into Sn?N Bonds
The reaction of in situ generated arynes with stannylated imines to provide ortho-stannyl-aniline derivatives is reported. The readily prepared trimethylstannyl benzophenone imine is introduced as an efficient reagent to realize the aryne σ-insertion reaction. The imine functionality is an established N-protecting group and insertions proceed with good yields and good to excellent regioselectivities. The product anilines are valuable starting materials for follow-up chemistry thanks to the rich chemistry offered by the trimethylstannyl moiety.
Kran, Eva,Mück-Lichtenfeld, Christian,Daniliuc, Constantin G.,Studer, Armido
p. 9281 - 9285
(2021/05/31)

Ultrasonic promoted synthesis of Ag nanoparticle decorated thiourea-functionalized magnetic hydroxyapatite: A robust inorganic-organic hybrid nanocatalyst for oxidation and reduction reactions
In this research, ultrasonic synthesis is applied for the fabrication of a novel catalyst, based on immobilization of silver nanoparticles (AgNPs) on thiourea functionalized magnetic hydroxyapatite. A recoverable Ag nano-catalyst is constructed by decoration of AgNPs on the surface of thiourea modified magnetic hydroxyapatite. Magnetic hydroxyapatite is used as an organic-inorganic hybrid support for the catalyst. The organic-inorganic hybrid support is prepared by co-precipitation, followed by its surface modification through covalent functionalization of 1-(3,5-bis(trifluoromethyl)phenyl)-3-propyl)thiourea. The fabricated catalyst has been characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), powder X-ray diffraction (XRD), nuclear magnetic resonance (NMR), Fourier-transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA) and Brunauer-Emmett-Teller (BET) analysis. The nanoparticles are mostly tubular in shape and their particle sizes are smaller than 100 nm. This nanocatalyst shows efficient and robust catalytic activity in different reactions, including selective reduction of 4-nitrophenol (4NP) and oxidation of primary amines by applying NaBH4and urea hydrogen peroxide (UHP) as reagents, respectively. The catalyst shows good reusability in 10 sequential reaction runs.
Bahadorikhalili, Saeed,Arshadi, Hosein,Afrouzandeh, Zahra,Ma'mani, Leila
p. 8840 - 8848
(2020/06/08)

In situ-formed cobalt embedded into N-doped carbon as highly efficient and selective catalysts for the hydrogenation of halogenated nitrobenzenes under mild conditions
Inhibiting the dehalogenation is the main challenge when halogenated nitrobenzenes are hydrogenated using H2 as hydrogen source by heterogeneous catalysis. Herein, the earth-abundant cobalt embedded into N-doped carbon (Co@CN) catalysts were fabricated via one-pot pyrolysis of tannic acid, Co(NO3)2·6H2O and melamine, which can function as a highly efficient non-noble-metal-based heterogeneous catalyst for selective hydrogenation of halogenated nitrobenzenes. Chloroanilines, bromoanilines, and iodoanilines, including all regioisomers, could be obtained with excellent selectivity (typically >99 %) at 60 °C under 1 MPa H2, at almost complete conversion of the substrates. Additionally, Co@CN demonstrated excellent catalytic stability and could be reused at least five times without obvious loss of catalytic activity and selectivity. Therefore, the Co@CN catalyst exhibits vast potential for future industrial application in the selective hydrogenation of halogenated nitrobenzenes.
Cao, Yueling,Liu, Kangkai,Wu, Chen,Zhang, Hepeng,Zhang, Qiuyu
(2020/01/28)

In Situ Synthesized Silica-Supported Co@N-Doped Carbon as Highly Efficient and Reusable Catalysts for Selective Reduction of Halogenated Nitroaromatics
Silica-supported Co@N-doped carbon (Co@CN/SiO2) catalysts were first prepared by a one-step impregnation with a mixed solution of cobalt nitrate, glucose and urea, followed by in situ carbonization and reduction. The Co@CN/SiO2 catalysts were investigated for the selective reduction of nitro aromatics to the corresponding anilines using hydrazine hydrate. The Co@CN/SiO2-500 carbonized at 500 °C exhibited the highest catalytic activity and excellent stability without any decay of activity after 6 cycles for the reduction of nitrobenzene. Both metallic Co atoms and Co?N species formed in the Co@CN/SiO2 catalysts were active, but the Co?N species were dominant active sites. The high activities of the Co@CN/SiO2 catalysts were attributed to the synergistic effect between the Co and N atoms, promoting heterolytic cleavage of hydrazine to form H+/H? pairs. Representative examples demonstrated that the Co@CN/SiO2-500 could completely transform various halogen-substituted nitro aromatics to the corresponding halogenated anilines with high TOFs and selectivity of '99.5 percent.
Sheng, Yao,Wang, Xueguang,Yue, Shengnan,Cheng, Gonglin,Zou, Xiujing,Lu, Xionggang
p. 4632 - 4641
(2020/07/30)

Chemoselective Hydrogenation of Nitroaromatics at the Nanoscale Iron(III)–OH–Platinum Interface
Catalytic hydrogenation of nitroaromatics is an environment-benign strategy to produce industrially important aniline intermediates. Herein, we report that Fe(OH)x deposition on Pt nanocrystals to give Fe(OH)x/Pt, enables the selective hydrogenation of nitro groups into amino groups without hydrogenating other functional groups on the aromatic ring. The unique catalytic behavior is identified to be associated with the FeIII-OH-Pt interfaces. While H2 activation occurs on exposed Pt atoms to ensure the high activity, the high selectivity towards the production of substituted aniline originates from the FeIII-OH-Pt interfaces. In situ IR, X-ray photoelectron spectroscopy (XPS), and isotope effect studies reveal that the Fe3+/Fe2+ redox couple facilitates the hydrodeoxygenation of the -NO2 group during hydrogenation catalysis. Benefitting from FeIII-OH-Pt interfaces, the Fe(OH)x/Pt catalysts exhibit high catalytic performance towards a broad range of substituted nitroarenes.
Fu, Gang,Li, Laiyang,Ming, Jiang,Qin, Ruixuan,Ren, Juan,Wang, Yongke,Wang, Yu,Zhang, Wuyong,Zheng, Nanfeng,Zhou, Wenting
supporting information
p. 12736 - 12740
(2020/06/01)

Isothiourea-Catalyzed Atroposelective N-Acylation of Sulfonamides
We report herein an atroposelective N-acylation of sulfonamides using a commercially available isothiourea catalyst, (S)-HBTM, with a simple procedure. The N-sulfonyl anilide products can be obtained in good to high enantiopurity, which represents a new axially chiral scaffold. The application of the product as a chiral iodine catalyst is also demonstrated for the asymmetric α-oxytosylation of propiophenone.
Ong, Jun-Yang,Ng, Xiao Qian,Lu, Shenci,Zhao, Yu
supporting information
p. 6447 - 6451
(2020/09/02)

AN IMPROVED ONE POT, ONE STEP PROCESS FOR THE HALOGENATION OF AROMATICS USING SOLID ACID CATALYSTS
The present invention disclosed an improved one pot, one step process for halogenation of compound of formula (II) to afford corresponding halogenated compound of formula (I) having improved yield and increased selectivity under very mild conditions.
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(2019/04/18)

A novel approach towards chemoselective reduction of nitro to amine
Chemo selective reduction of a wide range of aromatic nitro compound has been performed by using inexpensive Zn powder and CuSO4 system in water medium at room temperature. This system has high tolerance to other highly reducible groups present in nitro substance along with high conversation and selectivity. This chemo-selective reduction also provides a facile root for the synthesis of other industrially important fine chemicals or biologically important compounds where other highly reducible groups are present in close proximity to the targeted nitro groups.
Dasgupta, Hridoydip Ranjan,Mukherjee, Suvodip,Ghosh, Pranab
supporting information

(2019/08/13)

Reduction of Nitroarenes to Anilines with a Benzothiazoline: Application to Enantioselective Synthesis of 2-Arylquinoline Derivatives
The metal-free reduction of nitroarenes to aniline derivatives was accomplished in a short time by using a benzothiazoline as the hydrogen donor in combination with a Bronsted acid. An enantioselective synthesis of 2-arylquinolines was achieved by using 1-aryl-3-(2-nitrophenyl)propan-1-ones as starting materials and a combination of a benzothiazoline and a chiral phosphoric acid.
Miyagawa, Masamichi,Yamamoto, Ryota,Kobayashi, Nanako,Akiyama, Takahiko
supporting information
p. 499 - 502
(2019/02/26)

Bi-functional catalyst of porous N-doped carbon with bimetallic FeCu for solvent-free resultant imines and hydrogenation of nitroarenes
The efficient and stable catalyst applied to the transformation of amines into the corresponding imines and hydrogenation of nitroarenes under mild reaction conditions is reported. The catalytic performance of porous N-doped carbon with FeCu (FeCu@NPC) catalyst are tested by aromatic alcohol-based N-alkylated of amines with solvent-free and hydrogenation of nitroarenes via N2H4·H2O. The results proved that the yield of these two reactions are all over 99.9% under optimum condition. Moreover, the synergistic effect of the catalyst for N-alkylated reaction was investigated through the kinetic study. The catalyst can be easily separated from reaction system by an external magnetism, and can be recycled and reutilized for at least 4 runs with conversions are all over 75%. The study of the catalyst indicated that it was suitable for the reactions in industry. Hence, the catalysis process by the inexpensive metals-based catalyst is green and sustainable.
Wang, Kaizhi,Gao, Wenbing,Jiang, Pengbo,Lan, Kai,Yang, Ming,Huang, Xiaokang,Ma, Lei,Niu, Fang,Li, Rong
p. 43 - 53
(2019/01/08)

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 0157-0159

(2019/01/23)

Intramolecular Hydroamination of Selenoalkynes to 2-Selenylindoles in the Absence of Catalyst
In this work, a series of 2-chalcogenylindoles was synthesized by an efficient methodology, starting from chalcogenoalkynes, including a previously unreported tellurium indole derivative. For the first time, these 2-substituted chalcogenylindoles were obtained in the absence of metal catalyst or base, under thermal conditions only. In addition, the results described herein represent a methodology with inverse regioselectivity for the chalcogen functionalization of indoles.
Coelho, Felipe L.,Gil, Eduarda S.,Gon?alves, Paulo F. B.,Campo, Leandra F.,Schneider, Paulo H.
supporting information
p. 8157 - 8162
(2019/05/29)

Selective Photocatalytic Synthesis of Haloanilines from Halonitrobenzenes over Multifunctional AuPt/Monolayer Titanate Nanosheet
Bimetallic alloy AuPt nanoclusters supported on monolayer H1.07Ti1.73O4·H2O nanosheets (AuPt/TN) jointly complete a rapid catalytic reaction toward hydrogenation of halonitrobenzene to haloaniline in methanol under ambient conditions using HCOONH4 as a hydrogen source. Especially, AuPt/TN with a Au/Pt molar ratio of 1:2 exhibits the high catalytic conversion efficiency for halonitrobenzene (>99%) with a high selectivity of haloaniline (>99%). In situ FTIR spectra suggest that the TN affords surface Br?nsted acid sites to chemisorb and activate the halonitrobenzene molecules via the surface hydrogen bond coordination. In situ ESR experiments indicate that HCOONH4 would be decomposed to H+ and a ?CO2- radical by photogenerated holes, serving as the hydrogen source and reducing species for the reduction of the -NO2 group, respectively. Experimental results reveal that atom Pt in alloy is responsible for the hydrogenation, while Au represses the dehalogenation of haloanilines. Finally, a possible synergetic mechanism is discussed. This work highlights that the multifunctional AuPt/TN catalyst with multiple active sites exerts the respective functions to cooperatively catalyze organic transformations toward desired target products.
Song, Yujie,Wang, Huan,Wang, Zhitong,Guo, Binbin,Jing, Kaiqiang,Li, Yanjun,Wu, Ling
p. 9656 - 9664
(2018/10/02)

A robust core-shell nanostructured nickel-iron alloy@nitrogen-containing carbon catalyst for the highly efficient hydrogenation of nitroarenes
Currently, the catalytic selective hydrogenation of nitroarenes to produce aromatic amines is one of the most important key reactions in many fine chemical processes. In particular, non-noble-metal-catalyzed hydrogenation of nitroarenes represents more sustainable chemical processes. Here, we report a new robust and recyclable core-shell nanostructured nickel-iron alloy@nitrogen-containing carbon (NiFe@NC) catalyst and the beneficial effect of alloying Ni with Fe for the above reaction. The key to this synthetic strategy was thermally transforming the Ni-Fe layered double hydroxide (NiFe-LDH)/melamine mixture to form a fixed NiFe@NC nanostructure. A series of characterization results revealed the formation of NiFe alloy nanoparticles (NPs) coated with the NC overlayer. The as-fabricated NiFe@NC catalyst with a Ni/Fe atomic ratio of 3.0 exhibited superior activity for the reduction of the nitro group in o-chloronitrobenzene, with a 99.5% yield of o-chloroaniline under mild reaction conditions. The initial reaction rate over the catalyst was nearly three times that over the monometallic Ni@NC counterpart, and even one-order magnitude higher than that over pristine NiFe-LDH-derived NiFe alloy NPs. The extraordinary activity of NiFe@NC was reasonably attributed to the unique core-shell nanostructure, where both the NiFe alloy core and the NC overlayer shell could construct a significant promotional effect, being beneficial for the selective cleavage of the N-O bond. Recycling experiments indicated that the catalyst could be easily separated and recovered under an external magnetic field and experienced excellent recyclability during seventeen cycles without an obvious loss of catalytic activity. Furthermore, the present catalyst was also highly active for the chemoselective hydrogenation of other substituted nitroarenes bearing different functional groups to the corresponding anilines.
Zhang, Yaowen,Liu, Chunling,Fan, Guoli,Yang, Lan,Li, Feng
p. 13668 - 13679
(2018/10/15)

Rhodium-calix[4]pyrrole and rhodium-tetraphenyl porphyrin: preparation, surface grafting and their catalytic application in nitro-benzene reduction
Rhodium containing macromolecules calix[4]pyrrole (RhCP) and tetraphenyl porphyrin (RhTPP) were prepared and grafted on the surface of functionalised molecular sieve materials. 1H and 13C NMR, CHNS and mass spectral analyses were used for the structural elucidation of homogeneous organometallic complexes.1H NMR and CHNS analyses confirm the formation of calix[4]pyrrole (CP) and tetraphenyl porphyrin (TPP). The introduction of rhodium ions into the macromolecule is well evident from the disappearance of the 1H NMR signal characteristic of N-H proton (7.1 ppm in CP and ?2.74 ppm in TPP). Furthermore the formation of RhCP and RhTPP complexes is confirmed using CHNS and mass spectral analysis; the data are in line with theoretically calculated values. The grafting of RhCP and RhTPP on a diamino functionalised SBA-15 support was confirmed through low angle XRD, 13C MAS-NMR and SEM-EDAX analysis. Both homogeneous and heterogeneous catalysts were utilized for nitrobenzene reduction. RhCP and RhTPP heterogenized on SBA-15-F showed complete conversion of nitrobenzene with exclusive formation of aniline as a product. The catalytic activities were retained in both the systems even after several runs.
Ahmed, M.,Anjali, K.,Christopher, J.,Sakthivel, A.
p. 12353 - 12361
(2018/09/25)

Highly efficient and durable platinum nanocatalysts stabilized by thiol-terminated poly(N-isopropyl acrylomide) for selective hydrogenation of halonitrobenzene to haloaniline
In this paper, the selective hydrogenation of halonitrobenzenes (HNBs) to haloanilines (HANs) under mild conditions catalyzed by well-dispersed Pt nanoparticles protected by thiol-terminated poly(N-isopropyl acrylomide) (PNIPAM-SH) was firstly investigated. The polymer not only protected the Pt nanoparticles, but also inhibited the highly active Pt catalyst from producing undesired hydrodehalogenation products through anchoring the thiol groups to the surface of Pt nanoparticles. Thus high selectivities to HANs were achieved over this modified Pt catalyst for a variety of HNBs with satisfactory catalytic activities. Especially, the selectivity to HANs showed no obvious loss with the prolonging of the reaction time. Moreover, the recycling experiment showed that this Pt nanocatalyst was easier to recover and reuse based on the cononsolvency of PNIPAM-SH. Excellent stability and reusability were presented over this catalyst, and both the catalytic activity and selectivity were well maintained after fourteen runs.
Yu, Wenjun,Lou, Lan-Lan,Li, Shanshan,Ma, Tianyuan,Ouyang, Lezi,Feng, Li,Liu, Shuangxi
p. 751 - 757
(2017/01/12)

A Pd@Zeolite Catalyst for Nitroarene Hydrogenation with High Product Selectivity by Sterically Controlled Adsorption in the Zeolite Micropores
The adsorption of molecules on metal nanoparticles can be sterically controlled through the use of zeolite crystals, which enhances the product selectivity in hydrogenations of reactants with more than one reducible group. Key to this success was the fixation of Pd nanoparticles inside Beta zeolite crystals to form a defined structure (Pd@Beta). In the hydrogenation of substituted nitroarenes with multiple reducible groups as a model reaction, the Pd@Beta catalyst exhibited superior selectivity for hydrogenation of the nitro group, outperforming both conventional Pd nanoparticles supported on zeolite crystals and a commercial Pd/C catalyst. The extraordinary selectivity of Pd@Beta was attributed to the sterically selective adsorption of the nitroarenes on the Pd nanoparticles controlled by the zeolite micropores, as elucidated by competitive adsorption and adsorbate displacement tests. Importantly, this strategy is general and was extended to the synthesis of selective Pt and Ru catalysts by fixation inside Beta and mordenite zeolites.
Zhang, Jian,Wang, Liang,Shao, Yi,Wang, Yanqin,Gates, Bruce C.,Xiao, Feng-Shou
supporting information
p. 9747 - 9751
(2017/08/08)

Preparation method of o-iodoaniline
The invention discloses a preparation method of o-iodoaniline. The synthesis route is represented by a formula in the invention. The preparation method possesses following advantages: raw material aniline is widely available and cheap, and is beneficial for industrialized utilization of the preparation method; in a certain solvent, sodium bicarbonate/I2 are used for preparing paraiodoaniline via direct iodination of aniline, and yield is high; paraiodoaniline is taken as a raw material, a certain catalyst is adopted, and rearrangement reaction is carried out so as to realize chemical conversion of paraiodoaniline into o-iodoaniline, processing steps are few, conditions are mild, and green environment-protection requirements are satisfied; and both paraiodoaniline and o-iodoaniline are preferable pharmaceutical intermediates.
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(2017/06/02)

Copper-catalysed aromatic-Finkelstein reactions with amine-based ligand systems
A new efficient and low-cost ligand, diethylenetriamine, has been utilised to promote the iodination of 16 different bromo-substrates via the copper catalysed Finkelstein halogen exchange reaction under mild conditions. In contrast to earlier methods, the use of inert atmosphere conditions was not required to obtain high yields and purity. Studies on the speciation of the catalyst in solution indicate rapid disproportionation of copper(i) in the presence of diethylenetriamine to give copper(0) and a bis-ligated copper(ii) complex which is characterised by X-ray diffraction. This copper(ii) complex was also shown to be catalytically active in the halogen exchange reaction. In contrast, no significant disproportionation was observed using dimethylethylenediamine as the ligand, and the solid-state structures of a copper(i) dimeric complex and a 2D polymeric network of copper(i) iodide tetramers are reported. The catalytic activity of diethylenetriamine and dimethylethylenediamine with both copper(i) and copper(ii) salts are compared, and possible mechanistic implications discussed.
Jin, Xiaodong,Davies, Robert P.
p. 2110 - 2117
(2017/07/22)

Preparation method and application of hydrazide indoles drugs
The invention provides a preparation method and application of hydrazide indoles drugs, and discloses a 2-hydrazide substituted indole compound and a preparation method and application thereof. The novel 2-hydrazide substituted indole compound has quite high activity of inhibiting growth of tumor cells, and particularly has remarkable inhibiting effect on growth of human rectal cancer cells and colon cancer cells which have vascular endothelial growth factor receptor-2 subtype high expression; the IC50 value of the novel 2-hydrazide substituted indole compound can be about 10 mu M; the novel 2-hydrazide substituted indole compound has good antiangiogensis activity on a CAM (chick chorioallantoic membrane) model; and moreover, the compound 21 has good capability of resisting cell proliferation after HUVEC is stimulated by VEGF and specificity of resisting proliferation after HUVEC is simulated by VEGF.
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Paragraph 0037; 0038; 0041

(2017/08/28)

Sonication and Microwave-Assisted Primary Amination of Potassium- Aryltrifluoroborates and Phenylboronic Acids under Metal-Free Conditions
The transition-metal-free generation of a series of primary arylamines from potassium aryltrifluoroborates and phenylboronic acids- is reported. The method uses a mild, inexpensive source of nitrogen (hydroxylamine-O-sulfonic acid) in cooperation with aqueous sodium hydroxide in acetonitrile. Both a sonication and a microwave-assisted method were developed, which are capable of converting ArBF3K functionalities into primary arylamines (ArNH2) in isolated yields of up to 78% (10 examples for each method). This report represents the first general method for the conversion of aryltrifluoroborates into primary arylamines under mild, transition-metal-free conditions in moderate to very good yields. The method is applicable to a wide array of substrates containing electron-donating, electron-neutral, or electron-withdrawing substituents. Both the sonication and microwave methods were also applied to the generation of anilines from phenylboronic acids in isolated yields of up to 96% (12 examples for each method) that were superior to existing room temperature methods in terms of yield, while also offering much shorter reaction times (15 min vs 16 h). In particular, the microwave method is the first to allow for the conversion of arylboronic acids containing strongly electron-withdrawing substituents into the corresponding anilines in good yields, along with electron-donating- substituents in very good to excellent yields.
Kuik, Dale,McCubbin, J. Adam,Tranmer, Geoffrey K.
p. 2555 - 2561
(2017/05/22)

Highly chemoselective reduction of azides to amines by Fe(0) nanoparticles in water at room temperature
A highly chemoselective reduction of aryl, heteroaryl, acyl and sulfonyl azides to the corresponding amines has been achieved by Fe(0) nanoparticles in water at room temperature in the absence of external hydride source. Several readily reducible functionalities including alkene, alkyne, S-S linkage, OTBDMS remain unaffected during reduction.
Panja, Subir,kundu, Debasish,Ahammed, Sabir,Ranu, Brindaban C.
supporting information
p. 3457 - 3460
(2017/08/10)

Method for preparing o-haloaromaticamine from C-H-based activated arylamines
The invention belongs to the technical field of organic chemistry and particularly relates to a method for preparing o-haloaromaticamine from C-H-based activated arylamines. The method comprises the following steps: taking anhydrous copper acetate as a reaction catalyst and hydrogen peroxide as an oxidizing agent, adding aniline compounds and potassium bromide or potassium iodide into water for reaction at room temperature for 2 h, extracting with ethyl acetate and concentrating under reduced pressure, so as to obtain a corresponding arylamine halogenated compound crude product; and performing column chromatographic isolation and purification to obtain a corresponding purified product. The method has the characteristics that the operation is simple, reaction conditions are mild, the reaction time is short, and the method is environment-friendly.
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Paragraph 0029; 0030; 0031; 0032; 0033

(2017/07/22)

Novel method for preparing vortioxetine
The invention relates to a novel method for preparing vortioxetine. Reduction, nucleophilic substitution and coupling are conducted on a 2-nitroiodobenzene compound, and a compound of 1-[2-(2,4-dimethyl phenyl sulfanyl)-phenyl]methyl piperazine; then the obtained compound reacts with phenyl chloroformate to obtain 1-[2-(2,4-dimethyl phenyl sulfanyl)-phenyl]piperazine-1-carboxylic acid phenyl ester which generates vortioxetine after being hydrolyzed under the alkaline condition.
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Paragraph 0021

(2016/11/17)

Palladium-modified functionalized cyclodextrin as an efficient and recyclable catalyst for reduction of nitroarenes
A palladium-modified functionalized cyclodextrin (DACH-Pd-β-CD) catalytic system was synthesized and characterised. It showed high catalytic performance in the reduction of different nitroarenes to the corresponding anilines with the presence of sodium borohydride in water at room temperature. The yields of the desired products are up to 99%. Furthermore, the catalyst can be easily separated and still could maintain high catalytic activity after five cycles and no leaching of Pd into solution occurred.
Guo, Yafei,Li, Jiuling,Zhao, Fen,Lan, Guineng,Li, Liang,Liu, Yuqi,Si, Yunsen,Jiang, Yubo,Yang, Bo,Yang, Rui
p. 7950 - 7954
(2016/02/09)

Stable and reusable platinum nanocatalyst: An efficient chemoselective reduction of nitroarenes in water
Binaphthyl stabilized Pt nanoparticles (Pt-BNP) have been synthesized, characterized, and utilized as an efficient heterogeneous catalyst for chemoselective reduction of nitroarenes at room temperature in water. Several sensitive functional groups like ketone, ester, acid, amide, halides, and nitrile were well tolerated in this chemoselective reduction. The Pt-BNP catalyst was quantitatively recovered without any major change in particle size and reactivity and then efficiently reused for five catalytic cycles.
Kotha, Surya Srinivas,Sharma, Nidhi,Sekar, Govindasamy
supporting information
p. 1410 - 1413
(2016/03/12)

Efficient Catalytic System for Chemoselective Hydrogenation of Halonitrobenzene to Haloaniline Using PtZn Intermetallic Compound
Nanoparticulate intermetallic PtZn acts as a highly efficient heterogeneous catalyst for chemoselective hydrogenation of halonitrobenzenes to haloanilines. Chloroanilines, bromoanilines, and iodoanilines, including all regioisomers, were obtained with excellent yields (typically >99%) under 1 atm H2 at 40°C. A gram-scale reaction afforded a turnover number (TON) of 8600. PtZn/SiO2 could be reused at least four times without significant loss of catalytic performance. PtZn/SiO2 afforded 7-fold higher TOF than Pt/SiO2. A combination of kinetic analysis, X-ray photoelectron spectroscopy (XPS) studies, and density functional theory (DFT) calculations revealed that electron-enriched Pt by Zn not only promotes nitro-hydrogenation but also effectively inhibits the carbon-halogen bond scission.
Iihama, Sho,Furukawa, Shinya,Komatsu, Takayuki
p. 742 - 746
(2016/02/18)

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)

A base-mediated self-propagative Lossen rearrangement of hydroxamic acids for the efficient and facile synthesis of aromatic and aliphatic primary amines
A variety of aromatic and aliphatic hydroxamic acids were converted to the corresponding primary amines via base-mediated rearrangement. This rearrangement could proceed with less than 1 equiv. of K2CO3 in polar solvents under thermal conditions with no external reagents. This rearrangement has several features including no external activating agents needed for promoting the rearrangement, less than one equivalent of a base is sufficient for the reaction, and a clean reaction in which only carbon dioxide is produced as a by-product. A self-propagating mechanism via an isocyanate intermediate is proposed and elementary reaction steps, namely, chain propagation reactions are supported by experiments.
Ohtsuka, Naoya,Okuno, Moriaki,Hoshino, Yujiro,Honda, Kiyoshi
p. 9046 - 9054
(2016/10/05)

One-pot synthesis of primary amines from carboxylic acids through rearrangement of in situ generated hydroxamic acid derivatives
A one-pot synthesis of primary amines from carboxylic acids through a Lossen rearrangement of hydroxamic acid derivatives, which were in situ generated by the reaction of carboxylic acids with O-trimethylsilylhydroxylamine (NH2OTMS) and carbonyl diimidazole (CDI, 1.5 equiv) in dimethyl sulfoxide at room temperature, has been achieved. This one-pot method could be applied to various carboxylic acids such as aromatic, heteroaromatic, aliphatic, and optically active substrates.
Hoshino, Yujiro,Ohtsuka, Naoya,Okada, Takuya,Honda, Kiyoshi
p. 5304 - 5307
(2016/11/16)

Revisiting the Gold-Catalyzed Dimerization of 2-Ethynylanilines: A Room-Temperature and Silver-Free Protocol for the Synthesis of Multifunctional Quinolines
A room temperature and silver-free protocol for the formation of quinolines from 2-ethynylanilines through a dimerization event was achieved using a dinuclear gold catalyst, Au2(BIPHEP)(NTf2)2. The reaction is inherently modular, allowing for the incorporation of peripheral substituents at any site of the quinoline product. The reaction is readily applied to other heterocyles also as exemplified by the preparation of naphthyridines. Competition reactions to determine the reactivity of dissimilar alkynes demonstrated that the product ratio of dimerization vs intermolecular addition is rather dependent on the electronic nature of aryl substituent on the alkynes. However, control experiments with substrates possessing internal alkynes resulted in cycloisomerization instead of expected dimerization, which is indicative of possible steric influence of the alkyne terminus in the reaction outcome.
Praveen, Chandrasekar,Perumal
p. 855 - 864
(2016/03/15)

One-Pot Access to Benzo[a]carbazoles via Palladium(II)-Catalyzed Hetero- and Carboannulations
A Pd(II)-catalyzed direct synthesis of benzo[a]carbazoles has been achieved through aminopalladation of alkynes, followed by intramolecular nucleophilic addition of the generated carbon-palladium bond to a tethered cyano/aldehyde group. Compared to literature procedures, this synthetic approach is operationally simple, uses simple substrates, and offers a fast intramolecular assembly resulting in the direct synthesis of benzo[a]carbazoles in which a wide variation of substituents at different sites is well-tolerated, leaving enough opportunity for diversification.
Jash, Moumita,Das, Bimolendu,Chowdhury, Chinmay
supporting information
p. 10987 - 10999
(2016/11/28)

Synthesis of Pt nanocatalysts for selective hydrogenation of ortho-halogenated nitrobenzene
Monodisperse Pt nanoparticles (NPs) were prepared by reduction of platinum acetylacetonate in octadecene with the presence of Fe(CO)5. The synthesized nanocatalysts presented high activity and selectively for hydrogenation of ortho-halogenated nitrobenzene to the corresponding ortho-halogenated aniline under mild reaction conditions.
Xie, Ruigang,Cao, Xueqin,Pan, Yue,Gu, Hongwei
p. 1051 - 1055
(2015/03/30)

Indium(III)-Catalyzed Reduction of Nitrobenzenes to Anilines: Scope and Limitations
We have demonstrated that a combination of indium(III) iodide and 1,1,3,3-tetramethyldisiloxane (TMDS) effectively catalyzes the chemoselective reduction of nitrobenzenes with a variety of functional groups (halogens, alkyl, alkoxy, hydroxy, ester, amino, amide, cyanide, thiol, and an alkene moiety), producing the corresponding aniline derivatives.
Sakai, Norio,Asama, Shun,Konakahara, Takeo,Ogiwara, Yohei
p. 3179 - 3185
(2015/10/19)

Metal and base free synthesis of primary amines via ipso amination of organoboronic acids mediated by [bis(trifluoroacetoxy)iodo]benzene (PIFA)
A metal and base free synthesis of primary amines has been developed at ambient temperature through ipso amination of diversely functionalized organoboronic acids, employing a combination of [bis(trifluoroacetoxy)iodo]benzene (PIFA)-N-bromosuccinimide (NBS) and methoxyamine hydrochloride as the aminating reagent. The amines were primarily obtained as their trifluoroacetate salts which on subsequent aqueous alkaline work up provided the corresponding free amines. The combination of PIFA-NBS is found to be the mildest choice compared to the commonly used strong bases (e.g. n-BuLi, Cs2CO3) for activating the aminating agent. The reaction is expected to proceed via activation of the aminating reagent followed by B-N 1,2-aryl migration.
Chatterjee, Nachiketa,Goswami, Avijit
supporting information
p. 7940 - 7945
(2015/07/27)

Self-propagated Lossen rearrangement induced by a catalytic amount of activating agents under mild conditions
A mild self-propagated Lossen rearrangement induced by a catalytic amount of activating agents in medium to high polar organic solvents has been developed. The rearrangement of aromatic and aliphatic hydroxamic acids in the presence of a catalytic amount (0.01 equiv) of acetic anhydride and an equimolar amount of base such as well-dried potassium carbonate afforded the corresponding amines in high yields. This alternative to traditional Lossen rearrangement provides a simple and mild method for the synthesis of amines from free hydroxamic acids.
Hoshino, Yujiro,Shimbo, Yuki,Ohtsuka, Naoya,Honda, Kiyoshi
supporting information
p. 710 - 712
(2015/01/30)

A highly regioselective synthesis of N-acyl-2-acyl(aroyl)indolium Chloride through Palladium-Copper Catalysis Followed by Friedel-Crafts Reaction
2-Trimethylsilylethynyl acetanilides, obtained from the palladium-catalyzed reactions of 2-iodoacetanilides with trimethylsilylacetylene, underwent Friedel-Crafts acylation reactions yielding the N-acyl-2-acyl(aroyl)indolium chlorides in good yields. Georg Thieme Verlag Stuttgart New York.
Khan, Md. Wahab,Akther, Arifa,Alam, Md. Shariful
p. 831 - 834
(2014/04/17)

Polymethylhydrosiloxane derived palladium nanoparticles for chemo- and regioselective hydrogenation of aliphatic and aromatic nitro compounds in water
Chemo- and regioselective hydrogenation of a wide range of aliphatic, unsaturated, aromatic and heteroaromatic nitro compounds into their corresponding amines has been achieved with highly efficient polysiloxane-stabilised "Pd" nanoparticles on NAP-magnesium oxide supports using an environmentally friendly hydrogenating agent, polymethylhydrosiloxane [PMHS] in water. Highly stable and active Pd nanoparticles were prepared by the reduction of NAP-Mg-PdCl4 with PMHS, which serves as a reducing agent as well as a capping agent. The well-dispersed palladium nanoparticles on NAP-MgO catalysts also exhibit excellent regioselectivity in the hydrogenation of dinitrobenzenes to the corresponding nitroanilines. The catalyst has high durability against sintering during the hydrogenation reaction and can be reused with no loss in its activity. This journal is the Partner Organisations 2014.
Damodara, Dandu,Arundhathi, Racha,Ramesh Babu, T. Venkata,Legan, Margaret K.,Kumpaty, Hephzibah J.,Likhar, Pravin R.
p. 22567 - 22574
(2014/06/23)

Room-temperature chemoselective reduction of nitro groups using non-noble metal nanocatalysts in water
Purely aqueous-phase chemoselective reduction of a wide range of aromatic and aliphatic nitro substrates has been performed in the presence of inexpensive Ni- and Co-based nanoparticle catalysts using hydrazine hydrate as a reducing agent at room temperature. Along with the observed high conversions and selectivities, the studied nanoparticle catalysts also exhibit a high tolerance to other highly reducible groups present in the nitro substrates. The development of these potential chemoselective reduction catalysts also provides a facile route for the synthesis of other industrially important fine chemicals or biologically important compounds, where other highly reducible groups are present in close proximity to the targeted nitro groups.
Rai, Rohit K.,Mahata, Arup,Mukhopadhyay, Sushobhan,Gupta, Sampa,Li, Pei-Zhou,Nguyen, Kim T.,Zhao, Yanli,Pathak, Biswarup,Singh, Sanjay K.
p. 2904 - 2909
(2014/04/03)

Silver nanoparticles embedded over mesoporous organic polymer as highly efficient and reusable nanocatalyst for the reduction of nitroarenes and aerobic oxidative esterification of alcohols
Silver nanoparticles (Ag-NPs) have been finely dispersed at the mesoporous organic polymer via post-synthetic chemical grafting over mesoporous poly-triallylamine (MPTA-1). The resulting Ag-MPTA-1 nanomaterial has been characterized by elemental analysis, powder x-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), UV-vis diffuse reflectance spectroscopy (DRS), thermogravimetric analysis (TGA), EPR spectroscopy and AAS elemental analysis. The Ag-MPTA-1 acts as an efficient heterogeneous nanocatalyst in the reduction of substituted nitrobenzenes via transfer hydrogenation. The material also showed excellent catalytic activity in one-step catalytic oxidative esterification of primary alcohols using molecular oxygen as a green oxidant. The catalyst is air-stable, inexpensive, easy to prepare and reused several times without significant decrease in activity and selectivity.
Salam, Noor,Banerjee, Biplab,Roy, Anupam Singha,Mondal, Paramita,Roy, Susmita,Bhaumik, Asim,Islam, Sk. Manirul
p. 184 - 194
(2014/05/06)

One-pot synthesis of N-aryl propargylamine from aromatic boronic acid, aqueous ammonia, and propargyl bromide under microwave-assisted conditions
A facile, one-pot synthesis of N-aryl propargylamine from aromatic boronic acid, aqueous ammonia, and propargyl bromide has been achieved under microwave-assisted conditions. The reactions can be smoothly completed within a total 10 min through a two-step procedure, including copper-catalyzed coupling of aromatic boronic acids with aqueous ammonia and following propargylation by propargyl bromide.
Jiang, Yu-Bo,Zhang, Wen-Sheng,Cheng, Hui-Ling,Liu, Yu-Qi,Yang, Rui
p. 779 - 782
(2014/06/09)