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Coupling of ortho-chloronitrobenzene hydrogenation with 1,4-butanediol dehydrogenation over Cu[sbnd]MgO catalysts: A hydrogen free process
Aiming at an efficient method for the hydrogenation of o-chloronitrobenzene to o-chloroaniline under hydrogen free environment, the reaction was coupled with 1,4-butanediol dehydrogenation over Cu[sbnd]MgO catalysts containing various amounts of copper lo
Reddy, Kannapu Hari Prasad,Suh, Young-Woong,Anand, Narani,Raju, Burri David,Rao, Kamaraju Seetha Rama
p. 21 - 25
(2017)
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A hybrid nanocomposite precursor route to synthesize dispersion-enhanced Ni catalysts for the selective hydrogenation of o-chloronitrobenzene
Highly-dispersed Ni nanoparticles over carbon nanotubes (CNTs) were successfully prepared from a hybrid nanocomposite of Ni-Al layered double hydroxide (NiAl-LDH) and poly acrylic acid (PAA) functionalized CNTs. The physicochemical properties of materials
Wang, Jia,Fan, Guoli,Li, Feng
p. 982 - 991
(2013)
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Nickel Boride Catalyzed Reductions of Nitro Compounds and Azides: Nanocellulose-Supported Catalysts in Tandem Reactions
Nickel boride catalyst prepared in situ from NiCl2 and sodium borohydride allowed, in the presence of an aqueous solution of TEMPO-oxidized nanocellulose (0.01 wt%), the reduction of a wide range of nitroarenes and aliphatic nitro compounds. Here we describe how the modified nanocellulose has a stabilizing effect on the catalyst that enables low loading of the nickel salt pre-catalyst. Ni-B prepared in situ from a methanolic solution was also used to develop a greener and facile reduction of organic azides, offering a substantially lowered catalyst loading with respect to reported methods in the literature. Both aromatic and aliphatic azides were reduced, and the protocol is compatible with a one-pot Boc-protection of the obtained amine yielding the corresponding carbamates. Finally, bacterial crystalline nanocellulose was chosen as a support for the Ni-B catalyst to allow an easy recovery step of the catalyst and its recyclability for new reduction cycles.
Proietti, Giampiero,Prathap, Kaniraj Jeya,Ye, Xinchen,Olsson, Richard T.,Dinér, Peter
supporting information
p. 133 - 146
(2021/11/04)

Industrial Cunninghamia lanceolata carbon supported FeO(OH) nanoparticles-catalyzed hydrogenation of nitroarenes
The development of green and efficient methods for hydrogenation of nitroarenes is still highly demanding in organic synthesis. Herein, we report an industrial Cunninghamia lanceolata carbon supported FeO(OH) nanoparticles process for the synthesis of aryl amines with good yields via hydrogenation of nitroarenes. Nine key anti-cancer drug intermediates were successfully achieved with protocol. And Osimertinib intermediate 4m can be smoothly synthesized at a 2.67 kg-scale with >99.5% HPLC purity. This protocol features cheap carbon source, highly catalytic activity, simple operation, kilogram-scalable and recyclable catalysts (eight times without observable losing activity).
Fu, Lihua,Li, Dingzhong,Lu, Hao,Qiu, Renhua,Sun, Tulai,Xing, Chen,Yang, Tianbao
(2022/01/11)

Palladium Immobilized on a Polyimide Covalent Organic Framework: An Efficient and Recyclable Heterogeneous Catalyst for the Suzuki–Miyaura Coupling Reaction and Nitroarene Reduction in Water
An efficient and recyclable Pd nano-catalyst was developed via immobilization of Pd nanoparticles on polyimide linked covalent organic frameworks (PCOFs) that was facilely prepared through condensation of melamine and 3,3′,4,4′-biphenyltetracarboxylic dianhydride. The Pd nanoparticles (Pd NPs) catalyst was thoroughly characterized by FT-IR, XRD, SEM, TEM. Furthermore, the catalytic activity of Pd NPs catalyst was evaluated by Suzuki–Miyaura coupling reaction and nitroarene reduction in water, respectively. The excellent yields of corresponding products revealing revealed that the Pd NPs catalyst could be applied as an efficient and reusable heterogeneous catalyst for above two reactions. Graphical Abstract: [Figure not available: see fulltext.]
Dong, Zhenhua,Pan, Hongguo,Gao, Pengwei,Xiao, Yongmei,Fan, Lulu,Chen, Jing,Wang, Wentao
p. 299 - 306
(2021/05/10)

Halogenated method of aromatic compound
The invention belongs to the field of organic synthesis, and particularly relates to synthesis of aromatic halogens, in particular to arylamine. The invention discloses a synthesis method of a corresponding ortho-halogenated product from aromatic compounds such as carbazole and phenol. The method comprises the following steps: adding a metal sulfonate salt catalyst, aromatic amine, carbazole, phenol and other hydrogen - heteroatom-containing aromatic compound reaction substrates, a halogenation reagent and a reaction solvent at a specific reaction temperature. After the drying agent is dried, the yield of the reaction product and the nuclear magnetic characterization determining structure are determined by column chromatography. The reaction product yield is determined by gas chromatography. By adopting the method, under the cheap metal salt catalyst, a plurality of ortho-substituted brominated and chloro products can be obtained with moderate to excellent yield.
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(2021/11/10)

Synthesis method of metolachlor intermediate
The synthesis method comprises the following steps: S1) nitration reaction of chlorobenzene in a nitration reagent to obtain a mixture of o-chloronitrobenzene and p-chloronitrobenzene without separation. S2) The mixture of o-chloronitrobenzene and p-chloronitrobenzene is subjected to catalytic hydrogenation reaction to obtain the mixture of o-chloroaniline and p-chloroaniline, and the product does not need to be separated. S3) The mixture of o-chloroaniline and chloroaniline is subjected to diazotization reaction to obtain the mixture of o-chlorophenylhydrazine and p-chlorophenylhydrazine, and the product does not need to be separated. S4) The mixture of o-chlorophenylhydrazine and p-chlorophenylhydrazine and aldehyde are subjected to a condensation reaction to obtain a triazole ring mixture of Formulae I through a and I through b. S5) The triazole ring mixture is subjected to chlorination reaction to obtain the metolachlor intermediate shown in the formula I. 2, 4 - Dichloroaniline is used as a raw material, the production cost of the metolachlor is reduced, and the supply limitation of the raw material is avoided.
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(2021/09/21)

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)

Highly efficient N-doped carbon supported FeSx-Fe2O3 catalyst for hydrogenation of nitroarenes via pyrolysis of sulfurized N,Fe-containing MOFs
Integrating MOFs as precursor, especially for employing N-containing organic linkers, with sulfides is an effective method to prepare the highly efficient N-doped carbon supported metal-based catalysts for hydrogenation of nitroarenes. In this work, a N,Fe-containing metal organic frameworks (MOFs; termed as MIL88-HMTA) with spindle-like structure was prepared via self-assembly method, in which hexamethylenetetramine (HMTA) linker was introduced as N source. Subsequently, N-doped carbon supported FeSx-Fe2O3 catalyst (named FeSx-Fe2O3@CN) was fabricated upon the pyrolysis of sulfurized MIL88-HMTA. Catalytic experiments reveal that the FeSx-Fe2O3@CN delivered excellent performance for hydrogenation of nitroarenes in comparison with those of catalyst without sulfidation process (Fe2O3@CN) and conventional MIL88 derived catalyst (Fe2O3@C). The XRD, TEM, SEM/EDX, Raman, UV, and XPS analyses have revealed that the developed FeSx-Fe2O3@CN catalyst exhibited outstanding catalytic efficiency was ascribed to synergistic effect between FeSx and Fe2O3 species, abundant structural defects, more Fe-Nx species, and strengthened decomposition ability of hydrazine hydrate (N2H4?H2O). Furthermore, the effect of sulfidation ratio (the mass ratio between thioacetamide and MIL88-HMTA) towards preparation of the developed FeSx-Fe2O3@CN on the catalytic activity of hydrogenation reaction was also systematically performed. Notably, the optimized catalyst (denoted as FeSx-Fe2O3@CN-8) exhibited unexpected performance and recyclability for hydrogenation of nitroarenes under mild condition. The pyrolysis of sulfurized N-containing MOFs may present a facile approach for fabricating MOFs-derived N-doped carbon supported catalysts, which provides a potential application in heterogeneous catalytic reactions.
Li, Xuewei,She, Wei,Wang, Jing,Li, Weizuo,Li, Guangming
(2021/05/18)

Yeast supported gold nanoparticles: an efficient catalyst for the synthesis of commercially important aryl amines
Candida parapsilosisATCC 7330 supported gold nanoparticles (CpGNP), prepared by a simple and green method can selectively reduce nitroarenes and substituted nitroarenes with different functional groups like halides (-F, -Cl, -Br), olefins, esters and nitriles using sodium borohydride. The product aryl amines which are useful for the preparation of pharmaceuticals, polymers and agrochemicals were obtained in good yields (up to >95%) using CpGNP catalyst under mild conditions. The catalyst showed high recyclability (≥10 cycles) and is a robust free flowing powder, stored and used after eight months without any loss in catalytic activity.
Krishnan, Saravanan,Patel, Paresh N.,Balasubramanian, Kalpattu K.,Chadha, Anju
supporting information
p. 1915 - 1923
(2021/02/06)

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)

Development of sustainable and efficient nanocatalyst based on polyoxometalate/nickel oxide nanocomposite: A simple and recyclable catalyst for reduction of nitroaromatic compounds
In this paper, we report the synthesis and characterization of NiO@PolyMo nanocomposite. The newly synthesized nanocomposite was characterized by transmission electronmicroscopy (TEM), energy-dispersive X-ray spectroscopy (EDS), and powder X-ray diffraction (XRD). The particle sizes of the NiO@PolyMo nanocatalyst are in the range of 10–20 nm. Powder XRD patterns show that the phase of NiO@PolyMo remains unaltered even after the functionalization of NiO. The lattice fringes of d = 0.20 nm were observed, which correspond to the (111) plane of NiO phase. The newly synthesized material shows excellent catalytic performance and good selectivity for reduction of nitroarenes. The advantages of the present protocols are mild, and can be carried out using water as a solvent, which is an eco-friendly benign.
Kurbah, Sunshine Dominic
p. 1487 - 1495
(2021/04/22)

A suitable modified palladium immobilized on imidazolium supported ionic liquid catalysed transfer hydrogenation of nitroarenes
The first well-defined modified palladium immobilized on imidazolium supported ionic liquid catalyst has been developed for the transfer hydrogenation of nitroarenes to anilines in good to excellent yields with formic acid as reducing agent. This methodology applies eco-friendly a reducing agent which is non-toxic, water soluble, more stable and simpler to handle. Particularly, the process constitutes a rare model of base-free transfer hydrogenations. The catalyst was reused up to nine consecutive cycles without any significance loss in its activity.
Atheeswari, Alagudurai,Kanimozhi, Nallusamy,Karthikeyan, Parasuraman,Shanmugapriya, Ramasamy
(2021/06/28)

Novel mesoporous Ag@SiO2nanospheres as a heterogeneous catalyst with superior catalytic performance for hydrogenation of aromatic nitro compounds
Mesoporous core-shell structure Ag@SiO2 nanospheres are constructed to prevent Ag nanoparticles from aggregation during the hydrogenation reaction. The prepared catalyst shows superior catalytic performance for hydrogenation of nitro compounds with 100% conversion and selectivity without any by-products, which also indicates good recycling performance for several times use.
Lang, Leiming,Li, Wenyan,Lin, Xinying,Liu, Guangxiang,Long, Jing,Pan, Zhaorui,Zheng, Bo
p. 37708 - 37712
(2021/12/09)

Synthesis, Structure, and Catalytic Hydrogenation Activity of [NO]-Chelate Half-Sandwich Iridium Complexes with Schiff Base Ligands
A series of N,O-coordinate iridium(III) complexes with a half-sandwich motif bearing Schiff base ligands for catalytic hydrogenation of nitro and carbonyl substrates have been synthesized. All iridium complexes showed efficient catalytic activity for the hydrogenation of ketones, aldehydes, and nitro-containing compounds using clean H2 as reducing reagent. The iridium catalyst displayed the highest TON values of 960 and 950 in the hydrogenation of carbonyl and nitro substrates, respectively. Various types of substrates with different substituted groups afforded corresponding products in excellent yields. All N,O-coordinate iridium(III) complexes 1-4 were well characterized by IR, NMR, HRMS, and elemental analysis. The molecular structure of complex 1 was further characterized by single-crystal X-ray determination.
Lv, Wen-Rui,Li, Rong-Jian,Liu, Zhen-Jiang,Jin, Yan,Yao, Zi-Jian
p. 8181 - 8188
(2021/05/26)

Photocatalytic one-pot multidirectional N-alkylation over Pt/D-TiO2/Ti3C2: Ti3C2-based short-range directional charge transmission
Visible-light-induced one-pot, multistep, and chemoselectivity adjustable reactions highlight the economical, sustainable, and green process. Herein, we report Pt nanoparticles dispersed on S and N co-doped titanium dioxide/titanium carbide (MXene) (3%Pt/
Jiang, Heyan,Sheng, Meilin,Li, Yue,Kong, Shuzhen,Bian, Fengxia
(2021/05/17)

Minimization of Back-Electron Transfer Enables the Elusive sp3 C?H Functionalization of Secondary Anilines
Anilines are some of the most used class of substrates for application in photoinduced electron transfer. N,N-Dialkyl-derivatives enable radical generation α to the N-atom by oxidation followed by deprotonation. This approach is however elusive to monosubstituted anilines owing to fast back-electron transfer (BET). Here we demonstrate that BET can be minimised by using photoredox catalysis in the presence of an exogenous alkylamine. This approach synergistically aids aniline SET oxidation and then accelerates the following deprotonation. In this way, the generation of α-anilinoalkyl radicals is now possible and these species can be used in a general sense to achieve divergent sp3 C?H functionalization.
Zhao, Huaibo,Leonori, Daniele
supporting information
p. 7669 - 7674
(2021/03/08)

Visible-light induced one-pot hydrogenation and amidation of nitroaromatics with carboxylic acids over 2D MXene-derived Pt/N-TiO2/Ti3C2
Pt nanoparticles supported on N doped titanium dioxide/titanium carbide (MXene) heterojunctions were employed as photocatalysts for the tandem reactions between aromatic nitro compounds and carboxylic acids to produce amide products. The 3%Pt/N-TiO2/Ti3C2 heterojunction was prepared by in situ grew TiO2 on Ti3C2 nanosheets and then N doped TiO2 with melamine, Pt nanoparticles with 3.3 nm mean diameter well dispersed on N-TiO2/Ti3C2. 3%Pt/N-TiO2/Ti3C2 had excellent amidation activity and chemoselectivity under visible-light irradiation. The elevated catalytic performance of 3%Pt/N-TiO2/Ti3C2 was owing to the improvement in photogenerated electron and hole separation efficiency through charge short-range directional transmission caused by the intimate contact between the TiO2 and the conductive Ti3C2. This direct hydrogenation along with amidation between nitroaromatics and carboxylic acids own actual merits in the amides produce with no harmful byproducts. In situ DRIFTS spectra verified that the amidation activation with visible light irradiation at 25 °C was much faster than heating.
Jiang, Heyan,Hu, Zujie,Gan, Chuan,Sun, Bin,Kong, Shuzhen,Bian, Fengxia
(2021/03/03)

Method for synthesizing heteroatom- substituted aromatic compound from styrene compound
The invention discloses a method for synthesizing a heteroatom-substituted aromatic compound from a styrene compound, which comprises the following steps of: mixing a styrene compound with a general formula (I) and a heteroatom-containing compound with a general formula (II), and reacting in the presence of an acid additive and an organic solvent to obtain a heteroatom-substituted compound with ageneral formula (III). According to the synthesis method disclosed by the invention, a large amount of styrene compounds are used as raw materials and react to generate aromatic amine or phenol compounds under the action of no metal catalysis; and compared with the traditional aromatic amine and phenol synthesis method, the method has the advantages of high yield, simple conditions, low waste discharge amount, no metal participation, simple reaction equipment, easiness in industrial production and the like.
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(2021/02/06)

The graphite-catalyzed: ipso -functionalization of arylboronic acids in an aqueous medium: metal-free access to phenols, anilines, nitroarenes, and haloarenes
An efficient, metal-free, and sustainable strategy has been described for the ipso-functionalization of phenylboronic acids using air as an oxidant in an aqueous medium. A range of carbon materials has been tested as carbocatalysts. To our surprise, graphite was found to be the best catalyst in terms of the turnover frequency. A broad range of valuable substituted aromatic compounds, i.e., phenols, anilines, nitroarenes, and haloarenes, has been prepared via the functionalization of the C-B bond into C-N, C-O, and many other C-X bonds. The vital role of the aromatic π-conjugation system of graphite in this protocol has been established and was observed via numerous analytic techniques. The heterogeneous nature of graphite facilitates the high recyclability of the carbocatalyst. This effective and easy system provides a multipurpose approach for the production of valuable substituted aromatic compounds without using any metals, ligands, bases, or harsh oxidants.
Badgoti, Ranveer Singh,Dandia, Anshu,Parewa, Vijay,Rathore, Kuldeep S.,Saini, Pratibha,Sharma, Ruchi
p. 18040 - 18049
(2021/05/29)

A new ligand for copper-catalyzed amination of aryl halides to primary(hetero)aryl amines
N,N′-Bis(3,5-dimethoxyphenyl)cyclopentane-1,1-dicarboxamide was found as a new ligand for copper-catalyzed amination of aryl iodides, bromides and chlorides to afford various primary (hetero)aryl amines. These reactions proceeded efficiently under mild conditions when inexpensive aqueous ammonia (28% NH3 in H2O) was used as the amino source.
Chen, Dong,Dong, Xinrui,Jiang, Shang,Jiang, Sheng,Qiu, Yatao,Wu, Xiaoxing
supporting information

(2020/02/11)

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

Simple reversible fixation of a magnetic catalyst in a continuous flow system: Ultrafast reduction of nitroarenes and subsequent reductive amination using ammonia borane
Continuous reductive amination of aldehydes with nitroarenes over a Pd-Pt-Fe3O4 catalyst was performed. We used NH3BH3 as not only a hydrogen source for nitro reduction, but also a reductant for imine reduction. Secondary aromatic amines were obtained in the continuous flow reaction in good to excellent yields.
Byun, Sangmoon,Cho, Ahra,Kang, Dong Yun,Kim, B. Moon,Kim, Ha Joon,Kim, Hong Won,Kim, Seong Min,Lei, Cao,Park, Jin Kyoon
p. 944 - 949
(2020/03/11)

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

Pd stabilized on nanocomposite of halloysite and β-cyclodextrin derived carbon: An efficient catalyst for hydrogenation of nitroarene
Carbon nanospheres, CCDs, were fabricated using β-cyclodextrin as carbon precursor. The as prepared CCD was then hybridized with halloysite nanotubes (Hal) through hydrothermal treatment to furnish a nanocomposite, Hal-CCD that was subsequently applied as
Sadjadi, Samahe,Ghoreyshi Kahangi, Fatemeh,Heravi, Majid M.
(2019/11/14)

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

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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Page/Page column 0064

(2019/04/18)

Eco-friendly hydrogenation of aryl azides to primary amines on graphene oxide-decorated bimetallic Rh-Pt nanoparticles (RhPt@GO NPs)
Graphene oxide-supported rhodium/platinum (Rh-Pt) nanoparticles (Rh-Pt@GO NPs) are a promising catalyst for the reduction of aryl azides to primary amines. Rh-Pt@GO NPs have been produced by the microwave-assisted sonochemical method. This catalyst showed superior catalytic activity to afford quantitative yields of primary amines under an extremely mild condition in the presence of sodium borohydride. The synthesized novel catalyst was easily recovered by centrifugation and reused without loss of its catalytic activity. The spectroscopic analyses of the RhPt@GO NPs indicated the formation of highly crystalline, monodisperse, and colloidally stable RhPt@GO NPs.
Kilbas, Benan,Kara, Belguzar Yasemin
p. 33 - 37
(2019/01/26)

Superior activity and selectivity of heterogenized cobalt catalysts for hydrogenation of nitroarenes
The development of improved catalysts for highly selective hydrogenation of nitroarenes is described. For this purpose Co nanoparticles were supported on ordered mesoporous carbon CMK-3 and characterized in detail. The optimal CMK-3-CoPc catalyst exhibits excellent hydrogenation activity for several (hetero)aromatic nitro compounds and yielded the corresponding anilines under mild conditions (40 °C, 20 bar H2).
Li, Wu,Artz, Jens,Broicher, Cornelia,Junge, Kathrin,Hartmann, Heinrich,Besmehn, Astrid,Palkovits, Regina,Beller, Matthias
p. 157 - 162
(2019/01/10)

Bifunctional Pincer Catalysts for Chemoselective Transfer Hydrogenation and Related Reactions
A comparative study on the chemoselective transfer hydrogenation of nitroarenes to anilines and related processes using FA as the hydrogen source is described; these processes are catalyzed by a series of pincer catalysts equipped with different functional groups in the secondary coordination sphere. Some new (4 and 5) as well as previously reported (1–3) catalysts belonging to the family of bifunctional PC(sp3)P pincer complexes were employed in this study The reported compounds exhibited remarkably different catalytic activity behavior, depending on the nature of the functional groups. Transfer hydrogenation of nitrobenzene with FA as a hydrogen source was probed using iridium complexes 3 or 4 as a catalyst. Under the same conditions, the analogous palladium complex was found to be useful for the selective amidation of aniline with light carboxylic acids.
Cohen, Shirel,Bilyachenko, Alexey N.,Gelman, Dmitri
p. 3203 - 3209
(2019/02/09)

Cobalt nanoparticles anchoring on nitrogen doped carbon with excellent performances for transfer hydrogenation of nitrocompounds to primary amines and N-substituted formamides with formic acid
Cobalt nanoparticles anchoring on nitrogen doped carbon derived from pyrolysis of a cobalt complex and chitosan were developed for reduction of nitrocompounds with neat formic acid to their corresponding amines or N-substituted formamides by switch of solvents. Characterization results revealed that most of the nitrogen atoms are present as graphitic N and pyridinic N as anchoring sites, and the cobalt nanoparticles are wrapped by nitrogen doped carbon layers, endowing the catalyst with excellent activity and superior reusability.
Zhang, Yuecheng,Cao, Pengwei,Zhang, Hong-Yu,Yin, Guohui,Zhao, Jiquan
(2019/07/08)

Hydroxyl Assisted Rhodium Catalyst Supported on Goethite Nanoflower for Chemoselective Catalytic Transfer Hydrogenation of Fully Converted Nitrostyrenes
Control of chemoselectivity is a special challenge for the reduction of nitroarenes bearing one or more unsaturated groups. Here, we report a flower-like Rh/α-FeOOH catalyst for the chemoselective hydrogenation of nitrostyrene to vinylaniline over full conversion, which benefits the new functionalized aminostyrene because the multisubstituted aminostyrenes are usually commercially unavailable. This catalyst does not only show desirable selectivity for the vinylanilines, but also exhibits the inertness to various other reducible groups over wide reaction duration. The catalytic selectivity for the reduction of the nitro group towards vinyl group was investigated by the control experiments and FT-IR analysis. We have found that the abundant hydroxyl groups in the α-FeOOH may contribute to the improvement of catalytic activity and selectivity. Furthermore, the catalyst exhibits excellent stability and keeps its catalytic performance even after 6 cycles. (Figure presented.).
Hu, Zenan,Ai, Yongjian,Liu, Lei,Zhou, Junjie,Zhang, Gang,Liu, Hongqi,Liu, Xiangyu,Liu, Zhibo,Hu, Jianshe,Sun, Hong-bin,Liang, Qionglin
supporting information
p. 3146 - 3154
(2019/05/10)

METHOD AND CATALYST FOR PREPARING ANILINE COMPOUNDS AND USE THEREOF
The present invention provides a method for preparing aniline compounds, and also provides a kind of catalyst and use thereof. This method for synthesizing an aniline compound in the invention includes following steps: use molybdenum oxide and activated carbon as catalyst, hydrazine hydrate as reducing agent, then reduce aromatic nitro compounds to aniline compounds. This method is green and high efficiency, and easy to be applied in industry.
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(2019/04/18)

Method for synthesizing aniline compound, catalyst and application thereof
The invention provides a method for synthesizing an aniline compound, and further provides a catalyst and an application thereof. The method for synthesizing the aniline compound includes the following steps: taking molybdenum-based oxide and activated carbon as catalysts; taking hydrazine hydrate as a reducing agent; and reducing an aromatic nitro compound to the aniline compound. The method forsynthesizing the aniline compound has the characteristics of green and high efficiency, easy industrial application and the like.
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(2019/04/17)

Hydrogenation of Functionalized Nitroarenes Catalyzed by Single-Phase Pyrite FeS2 Nanoparticles on N,S-Codoped Porous Carbon
Catalytic hydrogenation of nitroarenes is an industrially very important and environmentally friendly process for the production of anilines; however, highly chemoselective reduction of nitroarenes decorated with one or more reducible groups in a nitroarene molecule remains a challenge. Herein, a novel hybrid non-noble iron-based nanocatalyst (named as FeS2/NSC) was developed, which was prepared from biomass as C and N source together with inexpensive Fe(NO3)3 as Fe source through high-temperature pyrolysis in a straightforward and cost-effective procedure. Comprehensive characterization revealed that single-phase pyrite FeS2 nanoparticles with precisely defined composition and uniform size were homogeneously dispersed on N,S-codoped porous carbon with large specific surface area, hierarchical porous channels, and high pore volume. The resultant catalyst FeS2/NSC demonstrated good catalytic activity for hydrogenation of functionalized nitroarenes with good tolerance of various functional groups in water as a sustainable and green solvent. Compared with bulk pyrite FeS2 and other non-noble metal-based heterogeneous catalysts reported in the literature, a remarkably enhanced activity was observed under mild reaction conditions. More importantly, FeS2/NSC displayed exclusive chemoselectivity for the reduction of nitro groups for nitroarenes bearing varying readily reducible groups.
Duan, Yanan,Dong, Xiaosu,Song, Tao,Wang, Zhaozhan,Xiao, Jianliang,Yuan, Youzhu,Yang, Yong
(2019/09/13)

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

Chemoselective reduction of nitroarenes with hydrazine over a highly active alumina-supported cobalt nanocatalyst
A green and efficient procedure is reported for the chemoselective reduction of nitroarenes catalyzed by a highly active alumina-supported cobalt nanocatalyst in the presence of hydrazine hydrate. The nanocatalyst can be applied under mild reflux conditions for the synthesis of arlyamines in high yields. Moreover, the catalyst can be easily recovered by simple filtration and reused several times without obvious loss in its catalytic activity.
Albadi, Jalal,Samimi, Heshmat Allah,Jalali, Mehdi
p. 740 - 744
(2019/10/14)

One-Pot Synthesis of Heterobimetallic Metal–Organic Frameworks (MOFs) for Multifunctional Catalysis
A one-pot synthesis of bimetallic metal–organic frameworks (Co/Fe-MOFs) was achieved by treating stoichiometric amounts of Fe and Co salts with 2-aminoterephthalic acid (NH2-BDC). Monometallic Fe (catalyst A) and Co (catalyst F) were also prepared along with mixed-metal Fe/Co catalysts (B–E) by changing the Fe/Co ratio. For mixed-metal catalysts (B–E) SEM energy-dispersive X-ray (EDX) analysis confirmed the incorporation of both Fe and Co in the catalysts. However, a spindle-shaped morphology, typically known for the Fe-MIL-88B structure and confirmed by PXRD analysis, was only observed for catalysts A–D. To test the catalytic potential of mixed-metal MOFs, reduction of nitroarenes was selected as a benchmark reaction. Incorporation of Co enhanced the activity of the catalysts compared with the parent NH2-BDC-Fe catalyst. These MOFs were also tested as electrocatalysts for the oxygen evolution reaction (OER) and the best activity was exhibited by mixed-metal Fe/Co-MOF (Fe/Co batch ratio=1). The catalyst provided a current density of 10 mA cm?2 at 410 mV overpotential, which is comparable to the benchmark OER catalyst (i.e., RuO2). Moreover, it showed long-term stability in 1 m KOH. In a third catalytic test, dehydrogenation of sodium borohydride showed high activity (turnover frequency=87 min?1) and hydrogen generation rate (67 L min?1 g?1 catalyst). This is the first example of the synthesis of bimetallic MOFs as multifunctional catalysts particularly for catalytic reduction of nitroarenes and dehydrogenation reactions.
Iqbal, Bushra,Saleem, Murtaza,Arshad, Salman Noshear,Rashid, Jamshaid,Hussain, Naveed,Zaheer, Muhammad
p. 10490 - 10498
(2019/07/15)

Electronic Modulation of Palladium in Metal Phosphide Nanoparticles for Chemoselective Reduction of Halogenated Nitrobenzenes
Tuning the electronic property of a transition metal plays an important role in the selective catalysis. Herein, the control synthesis of (PdxNiy)-P nanoparticles is reported. The binding energy of Pd3d5/2 as a function of
Zhao, Ming,Feng, Baoming,Qiao, Xiaofei,Zhong, Ning,Ge, Xuemei,Ji, Yuan
supporting information
p. 407 - 410
(2019/01/14)

Catalytic hydrogenation of carbonyl and nitro compounds using an [: N, O] -chelate half-sandwich ruthenium catalyst
A series of N,O-chelate half-sandwich ruthenium complexes for both carbonyl and nitro compound hydrogenation have been synthesized based on β-ketoamino ligands. All complexes exhibited high activity for the catalytic hydrogenation of a series of ketones and nitroarenes with molecular H2 as the reducing reagent in aqueous medium. Consequently, the catalytic system showed the catalytic TON values of 950 for 1-phenylethanol in acetophenone hydrogenation and 1960 for 1-chloro-4-nitrobenzene in p-chloroaniline hydrogenation. Good catalytic activity was displayed for various kinds of substrates with either electron-donating or electron-withdrawing groups. The neutral ruthenium complexes 1-4 were fully characterized using NMR, IR, and elemental analysis. Molecular structures of complexes 2 and 4 were further confirmed using single-crystal X-ray diffraction analysis.
Yao, Zi-Jian,Zhu, Jing-Wei,Lin, Nan,Qiao, Xin-Chao,Deng, Wei
p. 7158 - 7166
(2019/06/13)

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)

Michael addition reaction catalyzed by imidazolium chloride to protect amino groups and construct medium ring heterocycles
An effective approach for amino protection and construction of a seven-membered ring has been developed. The method uses imidazolium chloride to carry out the Michael addition reaction at low temperatures and perform amino deprotection or construction of a seven-membered ring at high temperatures.
Dai, Zeshu,Li, Dan,Li, Yanwu,Li, Zhiyao,Luo, Wen,Shang, Suqin,Tian, Qingqiang,Wang, Xuetong,Yuan, Jianyong,Zhang, Ying
supporting information

(2019/12/04)

Ru-Catalyzed Deoxygenative Transfer Hydrogenation of Amides to Amines with Formic Acid/Triethylamine
A ruthenium(II)-catalyzed deoxygenative transfer hydrogenation of amides to amines using HCO2H/NEt3 as the reducing agent is reported for the first time. The catalyst system consisting of [Ru(2-methylallyl)2(COD)], 1,1,1-tris(diphenylphosphinomethyl) ethane (triphos) and Bis(trifluoromethane sulfonimide) (HNTf2) performed well for deoxygenative reduction of various secondary and tertiary amides into the corresponding amines in high yields with excellent selectivities, and exhibits high tolerance toward functional groups including those that are reduction-sensitive. The choice of hydrogen source and acid co-catalyst is critical for catalysis. Mechanistic studies suggest that the reductive amination of the in situ generated alcohol and amine via borrowing hydrogen is the dominant pathway. (Figure presented.).
Pan, Yixiao,Luo, Zhenli,Xu, Xin,Zhao, Haoqiang,Han, Jiahong,Xu, Lijin,Fan, Qinghua,Xiao, Jianliang
supporting information
p. 3800 - 3806
(2019/07/12)

Atom-Economic Electron Donors for Photobiocatalytic Halogenations
In vitro cofactor supply and regeneration have been a major obstacle for biocatalytic processes, in particular on a large scale. Peroxidases often suffer from inactivation by their oxidative co-factor. Combining photocatalysis and biocatalysis offers an innovative solution to this problem, but lacks atom economy due to the sacrificial electron donors needed. Herein, we show that redox-active buffers or even water alone can serve as efficient, biocompatible electron sources, when combined with photocatalysis. Mechanistic investigations revealed first insights into the possibilities and limitations of this approach and allowed adjusting the reaction conditions to the specific needs of biocatalytic transformations. Proof-of-concept for the applicability of this photobiocatalytic reaction setup was given by enzymatic halogenations.
Seel, Catharina Julia,Králík, Antonín,Hacker, Melanie,Frank, Annika,K?nig, Burkhard,Gulder, Tanja
p. 3960 - 3963
(2018/09/25)

Highly efficient aqueous phase reduction of nitroarenes catalyzed by phosphine-decorated polymer immobilized ionic liquid stabilized PdNPs
Palladium nanoparticles stabilized by lightly cross-linked phosphine-decorated polymer immobilized ionic liquids (PIIL) and their PEGylated counterparts (PEGPIIL) are highly effective catalysts for the aqueous phase hydrogenation and sodium borohydride-based reduction of a wide range of nitroaromatic and heteroaromatic compounds under mild conditions with low catalyst loadings. Introduction of extensive cross-linking with tris(4-vinylphenyl)phosphine to isolate the phosphine-based heteroatom and limit the number of surface Pd?P interactions did not have a significant influence on catalyst performance. Comparative testing revealed PdNPs immobilized on lightly cross-linked phsophine-decoarted PEGylated polymer to be a highly efficient catalyst for the aqueous phase reduction of nitroarenes with a TON of 36000 (TOF = 2580 h-1) for hydrogenation and a TON of 274000 (TOF = 17125 h-1) for transfer hydrogenation. Even though these reactions occur under diffusion control due the poor solubility of the substrate these values are the highest to be reported for the room temperature aqueous phase reduction of nitroarenes catalyzed by a nanoparticle-based system. A continuous flow reduction of nitrobenzene in a packed bed reactor operated over a period of 250 min with no sign of catalyst deactivation and the corresponding space-time-yield of 0.738 g L-1 min-1 is a marked improvement on that of 0.384 g L-1 min-1 obtained in batch. The same system also catalyzes a tandem Suzuki-Miyaura cross coupling-nitroarene reduction sequence to afford high yields of biaryl amine in an operationally straightforward single-pot procedure. This is a highly versatile protocol which will enable the aromatic nitro fragment to be introduced as a nitro-substituted aryl or heteroaryl halide and as such will lend itself to rapid diversification for the synthesis of a wide range of amines.
Doherty,Knight,Backhouse,Bradford,Saunders,Bourne,Chamberlain,Stones,Clayton,Lovelock
p. 1454 - 1467
(2018/03/13)

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

Visible-light-driven Efficient Photocatalytic Reduction of Organic Azides to Amines over CdS Sheet–rGO Nanocomposite
CdS sheet–rGO nanocomposite as a heterogeneous photocatalyst enables visible-light-induced photocatalytic reduction of aromatic, heteroaromatic, aliphatic and sulfonyl azides to the corresponding amines using hydrazine hydrate as a reductant. The reaction shows excellent conversion and chemoselectivity towards the formation of the amine without self-photoactivated azo compounds. In the adopted strategy, CdS not only accelerates the formation of nitrene through photoactivation of azide but also enhances the decomposition of azide to a certain extent, which entirely suppressed formation of the azo compound. The developed CdS sheet-rGO nanocomposite catalyst is very active, providing excellent results under irradiation with a 40 W simple household CFL lamp.
Singha, Krishnadipti,Mondal, Aniruddha,Ghosh, Subhash Chandra,Panda, Asit Baran
p. 255 - 260
(2018/01/15)

A practical and highly efficient transfer hydrogenation of aryl azides using a [Ru(p-cymene)Cl2]2 catalyst and sodium borohydride
Various aniline derivatives were synthesized by selective reduction of aryl azides in the presence of a dichloro(p-cymene)ruthenium(II) dimer ([Ru(p-cymene)Cl2]2) via hydrolysis of sodium borohydride. The hydrogenation reactions were carried out in aqueous media at room temperature. Most of the reactions were completed within 10 min with quantitative yields.
Kilbas, Benan,Yilmaz, Yunus Emre,Ergen, Sinem
p. 880 - 883
(2018/08/21)

Selective hydrogenation of aromatic compounds using modified iridium nanoparticles
Till now, Ionic liquid-stabilized metal nanoparticles were investigated as catalytic materials, mostly in the hydrogenation of simple substrates like olefins or arenes. The adjustable hydrogenation products of aromatic compounds, including quinoline and relevant compounds, aromatic nitro compounds, aromatic ketones as well as aromatic aldehydes, are always of special interest, since they provide more choices for additional derivatization. Iridium nanoparticles (Ir NPs) were synthesized by the H2 reduction in imidazolium ionic liquid. TEM indicated that the Ir NPs is worm-like shape with the diameter around 12.2?nm and IR confirmed the modification of phosphine-functionalized ionic liquids (PFILs) to the Ir NPs. With the variation of the modifier, solvent and reaction temperature, substrate like quinoline and relevant compounds, aromatic nitro compounds, aromatic ketones as well as aromatic aldehydes could be hydrogenated by Ir NPs with interesting adjustable catalytic activity and chemoselectivity. Ir NPs modified by PFILs are simple and efficient catalysts in challenging chemoselective hydrogenation of quinoline and relevant compounds, aromatic nitro compounds, aromatic ketones as well as aromatic aldehydes. The activity and chemoselectivity of the Ir NPs could be obviously impacted or adjusted by altering the modifier, solvent and reaction temperature.
Jiang, He-Yan,Xu, Jie,Sun, Bin
(2018/01/27)

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
supporting information
p. 13668 - 13679
(2018/10/15)

Highly Selective Hydrogenation with Ionic Liquid Stabilized Nickel Nanoparticles
Abstract: Nickel nanoparticles (Ni NPs) were conveniently synthesized from the reduction of nickel(II) salt with NaBH4 or hydrazine in the presence of the ionic liquid 1-butyl-2,3-dimethylimidazolium (S)-2-pyrrolidinecarboxylic acid salt. UV/Vis spectroscopy, thermogravimetric analysis, and X-ray photoelectron spectroscopy were employed to characterize the interaction between the metal and the ionic liquid. The face-centered cubic structure of the Ni NPs(0) was confirmed by X-ray diffraction characterization. Transmission electron microscopy images revealed well-dispersed Ni particles of approximately 5.1?nm in average diameter. The ionic liquid immobilized Ni NPs were employed as highly efficient catalysts in chemoselective hydrogenation of quinoline and relevant compounds, as well as aromatic nitro compounds under mild reaction conditions. The Ni NPs can be efficiently recovered and reused. Graphical Abstract: [Figure not available: see fulltext.]
Jiang, He-yan,Zhang, Si-shi,Sun, Bin
p. 1336 - 1344
(2018/03/26)

Heterogeneous Iron-Catalyzed Hydrogenation of Nitroarenes under Water-Gas Shift Reaction Conditions
Reduction of various nitroarenes in the presence of heterogeneous iron oxide-based catalyst Fe 2 O 3 /NGr@C under water-gas shift reaction (WGSR) conditions has been demonstrated. The catalytic material is prepared in a straightforward manner via deposition/pyrolysis of iron-phenanthroline complex on carbon support. It shows high chemoselectivity towards the reduction of nitroarenes in the presence of other reducible and/or poisoning-capable functional groups. Hydrogenation is achieved using CO/H 2 O as a hydrogen source. Furthermore, it is demonstrated that the presence of triethylamine additive has a significant positive effect on the rate of reduction.
Ryabchuk, Pavel,Junge, Kathrin,Beller, Matthias
supporting information
p. 4369 - 4376
(2018/11/21)