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Synthesis and Biological Activity of 2-Arylidene- N -(quinolin-6-yl)hydrazine-1-carboxamides
A series of 2-arylidene-N-(quinolin-6-yl)hydrazine-1-carboxamides 5a-5o were synthesized and characterized. The synthesized compounds (5a-5o) were screened in vitro against three breast cancer cell lines: SKBR3, MDA-MB-231, and MCF-7 cancer cell lines by the MTT assay. According to MTT results, compounds 5k and 5l showed better antiproliferative activities over MCF-7 cell lines with IC50 values of 8.50 and 12.51 μM. Colony formation assay indicated 5k/5l treatment obviously inhibited the growth of MCF-7 cells and 5k/5l-induced cell cycle was arrested in the G2-M phase. Moreover, 5k/5l significantly increased the level of cleaved PARP and induced the apoptosis in MCF-7 cells. In addition, compared to Hela cells, MCF-7 cells were more sensitive to 5k/5l treatment.
Cao, Yin,Cui, Zhenzhen,Hu, Hongyu,Pan, Zhixiang,Zhang, Jiayun,Zhao, Shengxian
(2020)
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Enzymatic conversion of 6-nitroquinoline to the fluorophore 6-aminoquinoline selectively under hypoxic conditions
There is substantial interest in small molecules that can be used to detect or kill the hypoxic (low oxygen) cells found in solid tumors. Nitroaryl moieties are useful components in the design of hypoxia-selective imaging agents and prodrugs because one-electron reductases can convert the nitroaryl group to nitroso, hydroxylamino, and amino metabolites selectively under low oxygen conditions. Here, we describe the in vitro, cell free metabolism of a pro-fluorescent substrate, 6-nitroquinoline (1) under both aerobic and hypoxic conditions. Both LC-MS and fluorescence spectroscopic analyses provided evidence that the one-electron reducing enzyme system, xanthine/xanthine oxidase, converted the nonfluorescent parent compound 1 to the known fluorophore 6-aminoquinoline (2) selectively under hypoxic conditions. The presumed intermediate in this reduction process, 6-hydroxylaminoquinoline (6), is fluorescent and can be efficiently converted by xanthine/xanthine oxidase to 2 only under hypoxic conditions. This finding provides evidence for multiple oxygen-sensitive steps in the enzymatic conversion of nitroaryl compounds to the corresponding amino derivatives. In a side reaction that is separate from the bioreductive metabolism of 1, xanthine oxidase converted 1 to 6-nitroquinolin-2(1H)-one (5). These studies may enable the use of 1 as a fluorescent substrate for the detection and profiling of one-electron reductases in cell culture or biopsy samples. In addition, the compound may find use as a fluorogenic probe for the detection of hypoxia in tumor models. The occurrence of side products such as 5 in the enzymatic bioreduction of 1 underscores the importance of metabolite identification in the characterization of hypoxia-selective probes and drugs that employ nitroaryl units as oxygen sensors.
Rajapakse, Anuruddha,Linder, Collette,Morrison, Ryan D.,Sarkar, Ujjal,Leigh, Nathan D.,Barnes, Charles L.,Daniels, J. Scott,Gates, Kent S.
p. 555 - 563
(2013)
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A self-assembled delivery platform with post-production tunable release rate
Self-assembly of three molecular components results in a delivery platform, the release rate of which can be tuned after its production. A fluorophore-conjugated gelator can be hydrolyzed by an enzyme, resulting in the release of a fluorescent small molecule. To allow the release to be tunable, the enzyme is entrapped in liposomes and can be liberated by heating the system for a short period. Crucially, the heating time determines the amount of enzyme liberated; with that, the release rate can be tuned by the time of heating.
Boekhoven, Job,Koot, Mathijs,Wezendonk, Tim A.,Eelkema, Rienk,Van Esch, Jan H.
p. 12908 - 12911
(2012)
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Continuous and Selective Hydrogenation of Heterocyclic Nitroaromatics in a Micropacked Bed Reactor
The hydrogenation of heterocyclic nitroaromatics is of great importance in the pharmaceutical industry for the synthesis of key intermediates. However, high selectivity is difficult to achieve in conventional batch reactors owing to severe back mixing and poor mass transfer performance, resulting in the high requirement for subsequent separation processes. In this work, a continuous flow system based on a micropacked bed reactor is developed for the selective hydrogenation of heterocyclic nitroaromatics and the reductions of 5-nitroisoquinoline to 5-aminoisoquinoline and 5-amino-1,2,3,4-tetrahydroisoquinoline are selected as the model reactions. With the optimal reaction conditions, maximal yields of 99.9% (5-aminoisoquinoline) and 99.3% (5-amino-1,2,3,4-tetrahydroisoquinoline) are obtained successfully. Moreover, this system exhibits remarkable performance for the selective hydrogenation of relevant heterocyclic nitroaromatics with all yields beyond the level of 97.5%. The continuous flow system enables efficient hydrogenation of heterocyclic nitroaromatics and remarkable selectivity of target products with shorter reaction time and safer operation compared with batch reactors.
Chen, Xingkun,Duan, Xiaonan,Wang, Xuepeng,Zhang, Jisong
p. 2100 - 2109
(2021/09/08)

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

Hydrogenation reaction method
The invention relates to a hydrogenation reaction method, and belongs to the technical field of organic synthesis. The hydrogenation reaction method provided by the invention comprises the following steps: carrying out a hydrogen transfer reaction on a hydrogen acceptor compound, pinacol borane and a catalyst in a solvent in the presence of proton hydrogen, so that the hydrogen acceptor compound is subjected to a hydrogenation reaction; the catalyst is one or more than two of a palladium catalyst, an iridium catalyst and a rhodium catalyst; the hydrogen acceptor compound comprises one or morethan two functional groups of carbon-carbon double bonds, carbon-carbon triple bonds, carbon-oxygen double bonds, carbon-nitrogen double bonds, nitrogen-nitrogen double bonds, nitryl, carbon-nitrogentriple bonds and epoxy. The method is mild in reaction condition, easy to operate, high in yield, short in reaction time, wide in substrate application range, suitable for carbon-carbon double bonds,carbon-carbon triple bonds, carbon-oxygen double bonds, carbon-nitrogen double bonds, nitrogen-nitrogen double bonds, nitryl, carbon-nitrogen triple bonds and epoxy functional groups, good in selectivity and high in reaction specificity.
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Paragraph 0034; 0309-0312

(2020/05/14)

Generalized Chemoselective Transfer Hydrogenation/Hydrodeuteration
A generalized, simple and efficient transfer hydrogenation of unsaturated bonds has been developed using HBPin and various proton reagents as hydrogen sources. The substrates, including alkenes, alkynes, aromatic heterocycles, aldehydes, ketones, imines, azo, nitro, epoxy and nitrile compounds, are all applied to this catalytic system. Various groups, which cannot survive under the Pd/C/H2 combination, are tolerated. The activity of the reactants was studied and the trends are as follows: styrene'diphenylmethanimine'benzaldehyde'azobenzene'nitrobenzene'quinoline'acetophenone'benzonitrile. Substrates bearing two or more different unsaturated bonds were also investigated and transfer hydrogenation occurred with excellent chemoselectivity. Nano-palladium catalyst in situ generated from Pd(OAc)2 and HBPin extremely improved the TH efficiency. Furthermore, chemoselective anti-Markovnikov hydrodeuteration of terminal aromatic olefins was achieved using D2O and HBPin via in situ HD generation and discrimination. (Figure presented.).
Wang, Yong,Cao, Xinyi,Zhao, Leyao,Pi, Chao,Ji, Jingfei,Cui, Xiuling,Wu, Yangjie
supporting information
p. 4119 - 4129
(2020/08/10)

Palladium supported on metal–organic framework as a catalyst for the hydrogenation of nitroarenes under mild conditions
Sustainable development demands an environmentally friendly and efficient method for the hydrogenation of organic molecules, including the hydrogenation of functionalized nitroarenes. In this study, a highly active and selective metal–organic framework-supported palladium catalyst was prepared for the catalytic hydrogenation of nitroarenes. High selectivity (>99%) and excellent yield (98%) of aniline were realized after 2 hours in ethanol under hydrogen (1 atm) at room temperature. The reductions were successfully carried out in the presence of a wide range of other reducible functional groups. More importantly, the catalyst was very stable without the loss of its catalytic activity after five cycles.
Bao, Lingxiang,Fei, Teng,Li, Jiazhe,Pang, Siping,Sun, Chenghui,Yan, Zhiyuan,Yu, Zongbao
(2020/03/24)

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

Method for reducing aromatic nitro into arylamine
The invention relates to a method for reducing aromatic nitro to arylamine. The method comprises the following steps: (1) taking an aromatic nitro compound as a raw material, water as a hydrogen source, a palladium compound, cheap and easy to obtain, as a catalyst and tetrahydroxydiboron as an additive to reduce nitro to obtain a product; (2) taking the aromatic nitro compound as the raw material, a copper salt, cheap and easy to obtain, as the catalyst, the tetrahydroxydiboron as the additive to reduce the nitro to obtain a product; and (3) taking the aromatic nitro compound as the raw material, water as the hydrogen source, and the tetrahydroxydiboron as the additive, without needing a metal catalyst, to reduce the nitro to obtain a product. A preparation method for the arylamine, which is provided by the invention, is mild in reaction condition, low in costs, environment-friendly, high in yield, and suitable for industrial production.
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Paragraph 0193-0196; 0245-0248; 0285-0288

(2020/07/15)

Biomass-derived Fe-NC hybrid for hydrogenation with formic acid: Control of Fe-based nanoparticle distribution
A series of Fe-NC catalysts were synthesized by pyrolyzing an Fe complex and wheat flour at 500 °C. All of them were characterized and applied in the catalytic transfer hydrogenation of nitroarenes with formic acid. It was found that the catalytic activity was significantly affected by the size and distribution of Fe-based nanoparticles (NPs), which could be easily regulated by altering the Fe source. Meanwhile, more basic nitrogen sites were preserved on the catalyst so that the reaction ran smoothly without base additives. Among all catalysts, Fe-NC-FeCl2 exhibited the best catalytic performance due to smaller Fe3O4 NPs and greater N doping. Moreover, it showed excellent applicability for diverse nitroarenes. Obviously, this work demonstrates the importance of the metallic NPs' size and distribution, providing a new insight into the design of M-NC catalysts. The catalyst is economical and eco-friendly, and shows potential application value in industry.
Chen, Ligong,Gao, Ruixiao,Li, Yang,Liu, Lu,Wang, Bowei,Xu, Wensheng,Yan, Xilong,Zhang, Dan
p. 10689 - 10694
(2020/03/27)

Oxalic amide ligands, and uses thereof in copper-catalyzed coupling reaction of aryl halides
The present invention provides oxalic amide ligands and uses thereof in copper-catalyzed coupling reaction of aryl halides. Specifically, the present invention provides a use of a compound represented by formula I, wherein definitions of each group are described in the specification. The compound represented by formula I can be used as a ligand in copper-catalyzed coupling reaction of aryl halides for the formation of C—N, C—O and C—S bonds.
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Page/Page column 89-90

(2020/01/09)

HETEROCYCLIC CARBOXYLIC ACID AMIDE LIGAND AND APPLICATIONS THEREOF IN COPPER CATALYZED COUPLING REACTION OF ARYL HALOGENO SUBSTITUTE
Provided are a heterocyclic carboxylic acid amide ligand and applications thereof in a copper catalyzed coupling reaction. Specifically, provided are uses of a compound represented by formula (I), definitions of radical groups being described in the specifications. The compound represented by formula (I) can be used as the ligand in the copper catalyzed coupling reaction of the aryl halogeno substitute, and is used or catalyzing the coupling reaction for forming the aryl halogeno substitute having C—N, C—O, C—S and other bonds.
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Paragraph 0266-0267

(2019/05/15)

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)

Au@zirconium-phosphonate nanoparticles as an effective catalytic system for the chemoselective and switchable reduction of nitroarenes
In the present paper, a novel inorganic-organic layered material, a zirconium phosphate aminoethyl phosphonate, ZP(AEP), bearing aminoethyl groups on the layer surface, was used to immobilize AuNPs by a two-step procedure. The gold-based catalyst, Au1@ZP(AEP), containing 1 wt% Au, was characterized in terms of physico-chemical properties and TEM analysis revealed that the AuNPs have a spherical shape and an average size of 7.8 (±2.4) nm. Au1@ZP(AEP) proved its high efficiency for the chemoselective reduction of nitroarenes under mild conditions. Both batch and flow condition protocols have been defined. The catalytic system has been proven to be able to easily switch chemoselectivity allowing the control of the reduction of a series of nitroaromatics towards their corresponding azoxyarenes (2a-k) or anilines (2a-l) in 96% EtOH or abs EtOH, respectively, by using NaBH4 as a reducing agent, in good to excellent yields. Recovery and reuse of the catalytic system has been investigated proving the benefits of the flow approach.
Ferlin, Francesco,Cappelletti, Matteo,Vivani, Riccardo,Pica, Monica,Piermatti, Oriana,Vaccaro, Luigi
p. 614 - 626
(2019/02/13)

Sustainable Protocol for the Reduction of Nitroarenes by Heterogeneous Au@SBA-15 with NaBH4 under Flow Conditions
A gold-incorporated SBA-15 catalyst was prepared by a solvent-free ball-milling approach. The catalyst showed high reactivity and selectivity in the reduction of a variety of nitroarenes to anilines operating in absolute EtOH with NaBH4 as reducing agent. The catalyst was reused in batch conditions over five consecutive runs without any losses of activity or selectivity. Considering the high chemical stability and reusability of the catalytic system, a continuous-flow protocol was also investigated and defined to minimize the generation of waste and optimize the continuous reuse of the catalyst. Benefits of flow conditions were proven by turnover numbers that increased from 47.5 to 1902 and also by the minimization of both leaching (9.5 vs. 1 ppm) and E-factor values (8 vs. 23 in batch).
Ferlin, Francesco,Giannoni, Tommaso,Zuliani, Alessio,Piermatti, Oriana,Luque, Rafael,Vaccaro, Luigi
p. 3178 - 3184
(2019/02/19)

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

Visible-Light-Photocatalyzed Reductions of N-Heterocyclic Nitroaryls to Anilines Utilizing Ascorbic Acid Reductant
A photoreductive protocol utilizing [Ru(bpy)3]2+ photocatalyst, blue light LEDs, and ascorbic acid (AscH2) has been developed to reduce nitro N-heteroaryls to the corresponding anilines. Based on experimental and computational results and previous studies, we propose that the reaction proceeds via proton-coupled electron transfer between AscH2, photocatalyst, and the nitro N-heteroaryl. The method offers a green catalytic procedure to reduce, e.g., 4-/8-nitroquinolines to the corresponding aminoquinolines, substructures present in important antimalarial drugs.
Todorov, Aleksandar R.,Aikonen, Santeri,Muuronen, Mikko,Helaja, Juho
supporting information
p. 3764 - 3768
(2019/05/24)

Cobalt Entrapped in N,S-Codoped Porous Carbon: Catalysts for Transfer Hydrogenation with Formic Acid
Catalysts with Co nanoparticles (NPs) entrapped in N,S-codoped carbon shells were successfully fabricated by pyrolysis of porous organic polymers (POPs) with cobalt salts. The encapsulated structure consisting of Co NPs and N,S-codoped carbon layers was verified by TEM, XRD, and X-ray photoelectron spectroscopy. The catalysts displayed excellent activity and stability for the catalytic transfer hydrogenation (CTH) of nitrobenzene with formic acid under base-free conditions. Furthermore, the resultant catalysts allowed for highly efficient and selective transfer hydrogenation of various functionalized nitroarenes to the corresponding anilines. Through control experiments, the covered Co NPs were identified as active sites for CTH. The incorporation of S into the N-doped carbon lattice promoted the electron transfer from metallic cobalt NPs to their shells, which played a significant role in the acceleration of CTH. Moreover, the Co-NSPC-850 catalyst pyrolyzed at 850 °C showed excellent stability in the recycling experiments.
Guo, Haotian,Gao, Ruixiao,Sun, Mingming,Guo, Hao,Wang, Bowei,Chen, Ligong
p. 487 - 494
(2019/01/24)

Co based N, S co-doped carbon hybrids for catalytic hydrogenation: Role of cobalt salt and doped S
A series of Co-based N, S dual-doped carbon catalysts were prepared successfully via the pyrolysis of porous organic polymers (POPs)impregnated with cobalt salt and characterized by TEM, XRD, XPS, etc. The successful construction of cobalt-nitrogen (Co-Nx)sites is confirmed by XPS spectra. It was found that the content of Co-Nx sites is markedly affected by the type of cobalt salt, and the catalyst derived by the pyrolysis of the complex of POPs with Co(NO3)2·6H2O displays the best activity and outstanding selectivity for catalytic hydrogenation of various aromatic nitro compounds, it also demonstrates good recyclability. According to the results of control experiments, the activity for catalytic hydrogenation is mainly attributed to the Co-Nx sites. In addition, the doped S species in carbon shells can promote the formation of the active sites, which can effectively improve the performance of catalysts. Thus, this work can provide an effective and green approach for design highly effective transition metal-based multi-doped carbon catalysts with abundant metal-Nx sites.
Gao, Ruixiao,Guo, Haotian,Wang, Bowei,Qiu, Pengzhi,Sun, Mingming,Chen, Ligong
p. 99 - 105
(2019/05/28)

Divergent Late-Stage (Hetero)aryl C?H Amination by the Pyridinium Radical Cation
(Hetero)arylamines constitute some of the most prevalent functional molecules, especially as pharmaceuticals. However, structurally complex aromatics currently cannot be converted into arylamines, so instead, each product isomer must be assembled through a multistep synthesis from simpler building blocks. Herein, we describe a late-stage aryl C?H amination reaction for the synthesis of complex primary arylamines that other reactions cannot access directly. We show and rationalize through a mechanistic analysis the reasons for the wide substrate scope and the constitutional diversity of the reaction, which gives access to molecules that would not have been readily available otherwise.
Ham, Won Seok,Hillenbrand, Julius,Jacq, Jér?me,Genicot, Christophe,Ritter, Tobias
supporting information
p. 532 - 536
(2019/01/04)

Copper-catalyzed arene amination in pure aqueous ammonia
A simple protocol for copper-catalyzed arene amination using aqueous ammonia without any additional ligands and organic coordinating solvents has been developed. The reaction pathway via a Cu(i)/Cu(iii) mechanism is proposed based on the results of control experiments as well as DFT calculations.
Takagi, Mio,Watanabe, Ayako,Murata, Shigeo,Takita, Ryo
supporting information
p. 1791 - 1795
(2019/02/20)

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

Cu-catalyzed reduction of azaarenes and nitroaromatics with diboronic acid as reductant
A ligand-free copper-catalyzed reduction of azaarenes with diboronic acid as reductant in an aprotic solvent under mild conditions has been developed. Most interestingly, the nitroazaarenes could be reduced exclusively to give the corresponding amines without touching the azaarene moieties. Furthermore, the reductive amination of aromatic nitro compounds and aromatic aldehydes has also been realized. A series of hydrogenated azaarenes and secondary amines were obtained with good functional group tolerance.
Pi, Danwei,Zhou, Haifeng,Zhou, Yanmei,Liu, Qixing,He, Renke,Shen, Guanshuo,Uozumi, Yasuhiro
p. 2121 - 2129
(2018/03/23)

Metal-free Reduction of Nitro Aromatics to Amines with B 2 (OH) 4 /H 2 O
A metal-free reduction of nitro aromatics mediated by diboronic acid with water as both the hydrogen donor and solvent under mild conditions has been developed. A series of aromatic amines were obtained with good functional group tolerance and in good yields.
Chen, Danyi,Zhou, Yanmei,Zhou, Haifeng,Liu, Sensheng,Liu, Qixing,Zhang, Kaili,Uozumi, Yasuhiro
supporting information
p. 1765 - 1768
(2018/06/26)

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)

Enhanced catalytic performance of cobalt nanoparticles coated with a N,P-codoped carbon shell derived from biomass for transfer hydrogenation of functionalized nitroarenes
The development of abundantly available base metal catalysts for organic transformations remains an important goal of chemical research. Herein, we report the first facile fabrication of active, inexpensive, and reusable cobalt nanoparticles (NPs) coated with a N,P-codoped carbon shell derived from naturally renewable biomass and earth-abundant, low-cost cobalt salt and PPh3. The entire process is operationally simple, straightforward, cost-effective and environmentally benign and can be used in mass production for practical application. The resultant catalysts allow for highly efficient and selective transfer hydrogenation of functionalized nitroarenes to the corresponding anilines using formic acid or ammonium formate as the hydrogen donor. Uniformly incorporated N and P into the carbon lattices exhibited synergistic effects with the encapsulated Co NPs to engineer the structure and composition of the catalyst, thereby substantially boosting the catalytic efficiency. The most active catalyst Co@NPC-800 exhibited outstanding activity and exclusive selectivity for the reduction of functionalized nitroarenes to anilines, especially those decorated with readily reducible functional groups. The catalyst demonstrated high stability and can be easily separated by using an external magnet for successive reuses without significant loss in both activity and selectivity.
Duan, Yanan,Song, Tao,Dong, Xiaosu,Yang, Yong
supporting information
p. 2821 - 2828
(2018/06/29)

Copper mediated C-H amination with oximes: En route to primary anilines
Here we report an efficient Cu(i)-mediated C-H amination reaction with oximes as amino donors to introduce NH2 groups directly. Various strongly coordinating heterocycles including quinoline, pyrimidine, pyrazine, pyrazole and triazole were tolerated well. The potential utility was further demonstrated in a late-stage modification of telmisartan (an antagonist for the angiotensin II receptor).
Xu, Lin-Lin,Wang, Xing,Ma, Biao,Yin, Ming-Xing,Lin, Hai-Xia,Dai, Hui-Xiong,Yu, Jin-Quan
p. 5160 - 5164
(2018/06/21)

A 4, 4 - dimethoxy - 2, 2 - bipyridyl silver catalytic hydrogenation of aromatic nitro compound synthesis of aromatic amines (by machine translation)
The invention discloses a 4, 4 - dimethoxy - 2, 2 - bipyridyl silver catalytic hydrogenation of aromatic nitro compound synthesis of aromatic amines, the method uses a cheap, easy synthesis of 4, 4 - dimethoxy - 2, 2 - bipyridyl silver as catalyst, in order to green, environmental protection, non-toxic as the hydrogen source, the aromatic nitro compound in the relatively mild reaction conditions, one-step reaction can synthesize aromatic amine. The invention has simple operation, catalyst is cheap and easy and small consumption, mild reaction conditions, to substrate demonstrates better functional group tolerant, high product yield, industrial manufacturing cost, it has very good application prospect. (by machine translation)
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Paragraph 0016; 0033; 0036; 0041; 0044

(2017/07/19)

Copper-Based Intermetallic Electride Catalyst for Chemoselective Hydrogenation Reactions
The development of transition metal intermetallic compounds, in which active sites are incorporated in lattice frameworks, has great potential for modulating the local structure and the electronic properties of active sites, and enhancing the catalytic activity and stability. Here we report that a new copper-based intermetallic electride catalyst, LaCu0.67Si1.33, in which Cu sites activated by anionic electrons with low work function are atomically dispersed in the lattice framework and affords selective hydrogenation of nitroarenes with above 40-times higher turnover frequencies (TOFs up to 5084 h-1) than well-studied metal-loaded catalysts. Kinetic analysis utilizing isotope effect reveals that the cleavage of the H-H bond is the rate-determining step. Surprisingly, the high carrier density and low work function (LWF) properties of LaCu0.67Si1.33 enable the activation of hydrogen molecules with extreme low activation energy (Ea = 14.8 kJ·mol-1). Furthermore, preferential adsorption of nitroarenes via a nitro group is achieved by high oxygen affinity of LaCu0.67Si1.33 surface, resulting in high chemoselectivity. The present efficient catalyst can further trigger the hydrogenation of other oxygen-containing functional groups such as aldehydes and ketones with high activities. These findings demonstrate that the transition metals incorporated in the specific lattice site function as catalytically active centers and surpass the conventional metal-loaded catalysts in activity and stability.
Ye, Tian-Nan,Lu, Yangfan,Li, Jiang,Nakao, Takuya,Yang, Hongsheng,Tada, Tomofumi,Kitano, Masaaki,Hosono, Hideo
p. 17089 - 17097
(2017/12/06)

Carbonyl Iron Powder: A Reagent for Nitro Group Reductions under Aqueous Micellar Catalysis Conditions
An especially mild, safe, efficient, and environmentally responsible reduction of aromatic and heteroaromatic nitro-group-containing educts is reported that utilizes very inexpensive carbonyl iron powder (CIP), a highly active commercial grade of iron powder. These reductions are conducted in the presence of nanomicelles composed of TPGS-750-M in water, a recyclable aqueous micellar reaction medium. This new technology also shows broad scope and scalability and presents opportunities for multistep one-pot sequences involving this reducing agent.
Lee, Nicholas R.,Bikovtseva, Agata A.,Cortes-Clerget, Margery,Gallou, Fabrice,Lipshutz, Bruce H.
supporting information
p. 6518 - 6521
(2017/12/26)

Palladium nanoparticles stabilized by aqueous vesicles self-assembled from a PEGylated surfactant ionic liquid for the chemoselective reduction of nitroarenes
Vesicles self-assembled from an aqueous PEGylated surfactant ionic liquid solution can be applied for stabilizing palladium nanoparticles, which prove to be an efficient catalytic system for chemoselective hydrogen transfer of nitroarenes using hydrazine hydrate as a hydrogen source. The particle sizes of vesicles are decreased with the increase of ionic liquid's concentrations and relatively small particle sizes are beneficial to the reduction. Moreover, the aqueous catalytic system still stays in reactor by simple extraction, and is reused without further treatment.
Xu, Zhu-bing,Lu, Guo-ping,Cai, Chun
p. 57 - 60
(2017/06/06)

Water as a hydrogen source in palladium-catalyzed reduction and reductive amination of nitroarenes mediated by diboronic acid
An unprecedented palladium-catalyzed chemoselective reduction and reductive amination of nitroarenes with water as a hydrogen source mediated by diboronic acid have been discovered. A series of aryl amines containing various reducible functional groups were obtained in good to excellent yields.
Zhou, Yanmei,Zhou, Haifeng,Liu, Sensheng,Pi, Danwei,Shen, Guanshuo
p. 3898 - 3904
(2017/06/13)

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

Palladium Nanoparticles Stabilized by Metal–Carbon Covalent Bonds as an Expeditious Catalyst for the Oxidative Dehydrogenation of Nitrogen Heterocycles
The first method for the dehydrogenation of nitrogen heterocycles catalyzed by a palladium nanocatalyst was developed. Carbon–metal covalent-bond-stabilized nanoparticles were found to be efficient for the dehydrogenation process in the presence of tert-butyl hydroperoxide. A variety of N-heterocycles were transformed into functionalized quinolines in medium to excellent yields in water as the solvent under mild conditions by a simple operation.
Sun, Xiao-Tao,Zhu, Jie,Xia, Yun-Tao,Wu, Lei
p. 2463 - 2466
(2017/07/12)

One-pot synthesis of: N -substituted pyrroles from nitro compounds and 2,5-hexadione over a heterogeneous cobalt catalyst
In this study, the one-pot heterocyclization of nitro compounds with 2,5-hexadione was studied for the synthesis of N-substituted pyrroles via a Paal-Knorr condensation process. The heterogeneous cobalt-nitrogen catalyst (Co-Nx/C-800-AT) was found to be active for this reaction with formic acid. Formic acid served as a hydrogen donor for the transfer hydrogenation, and also acted as an acid catalyst. More importantly, this method was tolerant of other functional groups, and hence various N-substituted pyrroles were produced with good to excellent yields. The Co-Nx/C-800-AT catalyst was highly stable, and could be reused several times without loss of its catalytic activity.
Gong, Zheng,Lei, Yu,Zhou, Peng,Zhang, Zehui
p. 10613 - 10618
(2017/10/05)

Nickel-Catalyzed Cross-Coupling of Ammonia or Primary Alkylamines with (Hetero)aryl Sulfamates, Carbamates, or Pivalates
A catalyst system capable of effecting the cross-coupling of ammonia or primary alkylamines with (hetero)aryl sulfamates, carbamates, or pivalates is reported for the first time. The air-stable nickel(II) pre-catalyst C1 tolerates a broad spectrum of heterocyclic functionality within both reaction partners, as well as ether, nitrile, pyrrole, trifluoromethyl, and boronate ester substituents. In the case of reactions involving primary alkylamines and (hetero)aryl sulfamates and carbamates, room-temperature cross-couplings were achieved.
MacQueen, Preston M.,Stradiotto, Mark
supporting information
p. 1652 - 1656
(2017/08/11)

Nickel-Catalyzed Amination of Aryl Carbamates with Ammonia
Aryl carbamates were employed in the nickel-catalyzed monoarylation of ammonia. The applied, well-defined single-component nickel(II) precatalyst contains a Josiphos ligand, is air-stable, and operates without any ancillary reductant. This catalyst system
Schranck, Johannes,Furer, Patrick,Hartmann, Veronika,Tlili, Anis
supporting information
p. 3496 - 3500
(2017/07/04)

Discovery of N-(Naphthalen-1-yl)-N′-alkyl Oxalamide Ligands Enables Cu-Catalyzed Aryl Amination with High Turnovers
A class of N-(naphthalen-1-yl)-N′-alkyl oxalamides have been proven to be powerful ligands, making a coupling reaction of (hetero)aryl iodides with primary amines proceed at 50 °C with only 0.01 mol % of Cu2O and ligand as well as a coupling reaction of (hetero)aryl bromides with primary amines and ammonia at 80 °C with only 0.1 mol % of Cu2O and ligand. A wide range of coupling partners work well under these conditions, thereby providing an easy to operate method for preparing (hetero)aryl amines.
Gao, Jie,Bhunia, Subhajit,Wang, Kailiang,Gan, Lu,Xia, Shanghua,Ma, Dawei
supporting information
p. 2809 - 2812
(2017/06/07)

Continuous flow hydrogenation of nitroarenes, azides and alkenes using maghemite-Pd nanocomposites
Maghemite-supported ultra-fine Pd (1-3 nm) nanoparticles, prepared by a simple co-precipitation method, find application in the catalytic continuous flow hydrogenation of nitroarenes, azides, and alkenes wherein they play an important role in the reduction of various functional groups on the surface of maghemite with catalyst loading (~6 wt% Pd). The salient features of the protocol include expeditious formation of reduced products in high yields under near ambient conditions with recycling of the catalyst (up to 12 cycles) without any decrease in selectivity and yield.
Rathi, Anuj K.,Gawande, Manoj B.,Ranc, Vaclav,Pechousek, Jiri,Petr, Martin,Cepe, Klara,Varma, Rajender S.,Zboril, Radek
p. 152 - 160
(2015/12/31)

Metal-Free Reduction of Aromatic Nitro Compounds to Aromatic Amines with B2pin2 in Isopropanol
A metal-free reduction of aromatic nitro compounds to the corresponding amines has been achieved by a combination of B2pin2 and KOtBu in isopropanol. A series of nitro compounds containing various reducible functional groups were chemoselectively reduced in good to excellent yields.
Lu, Hongtao,Geng, Zhiyue,Li, Jingya,Zou, Dapeng,Wu, Yusheng,Wu, Yangjie
supporting information
p. 2774 - 2776
(2016/06/15)

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)

An abnormal N-heterocyclic carbene based nickel complex for catalytic reduction of nitroarenes
Herein we report the synthesis of a nickel(ii) dichloro complex bearing an abnormal N-heterocyclic carbene (aNHC). The NiCl2(aNHC)2 complex has been used as an efficient catalyst for the reduction of nitroarenes with hydrosilanes to give aromatic amines in good to excellent yields. This catalytic protocol can tolerate functional groups such as halides, alkenes or nitriles. Furthermore, the longevity of the catalyst was tested in successive catalytic cycles, which indicates a sustained catalytic activity over multiple catalytic cycles.
Vijaykumar, Gonela,Mandal, Swadhin K.
p. 7421 - 7426
(2016/06/01)

Cubical Palladium Nanoparticles on C@Fe3O4 for Nitro reduction, Suzuki-Miyaura Coupling and Sequential Reactions
Cubical Pd nanoparticles incorporated magnetically recyclable nanoreactor (Pd cNPs/C@Fe3O4) are found to be efficient catalysts for the hydrogenation or aromatic nitrocompounds, Suzuki-Miyaura coupling and the sequential reaction of [Formula presented] coupling followed by reduction of nitrobiphenyl substrates. A variety of aryl iodides, bromides and chlorides were coupled with phenylboronic acids to form corresponding biaryl products and variety of nitro aromatic compounds was hydrogenated with excellent yield and high TON. The catalytic activity of palladium cubical nanoparticles (Pd cNPs) embedded with excess of {100} surface facets are superior compared to Pd spherical nanoparticles (Pd sNPs) embedded with mixed surface facets. The catalytic efficiency remains unaltered even after five repeated cycles. The observed enhanced catalytic activity is attributed to the high density of low-coordinated Pd {100} atoms present at the surface of the Pd cNPs/C@Fe3O4 catalyst, confirmed by HR-TEM studies. Also, the catalyst is truly heterogeneous, highly stable, does not require any toxic ligands, has wide substrate scope in both nitroreduction and Suzuki-Miyaura coupling reaction along with the ability to catalyse in a sequential manner, magnetically separable from the reaction mixture and can be reused.
Kumar, Basuvaraj Suresh,Amali, Arlin Jose,Pitchumani, Kasi
p. 511 - 519
(2016/08/15)

A simple and efficient: In situ generated ruthenium catalyst for chemoselective transfer hydrogenation of nitroarenes: Kinetic and mechanistic studies and comparison with iridium systems
The catalytic activities of a series of in situ generated homogeneous ruthenium systems based on commercially available [RuCl2(p-cymene)]2 and various ligands in transfer hydrogenation of nitroarenes to anilines were investigated. Combination of [RuCl2(p-cymene)]2 and tridentate phenanthroline based ligand 2-(6-methoxypyridin-2-yl)-1,10-phenanthroline (phenpy-OMe) exhibited the highest catalytic activity for this reaction using 2-propanol as hydrogen source. This protocol provides a facile route to access aromatic amines under mild conditions in excellent yields. Notably, this system chemoselectively reduced the nitro groups over an array of other reactive functionalities such as ketone, alkene, amide, nitrile, and aryl halide. Operational simplicity, high yields, mild reaction conditions and short reaction times make this an attractive methodology for accessing various functionalized anilines. A series of controlled experiments and careful mechanistic investigation with the possible intermediates suggested that transformation of nitrobenzene to aniline with ruthenium and iridium system proceeded via direct route and condensation route respectively.
Paul, Bhaskar,Chakrabarti, Kaushik,Shee, Sujan,Maji, Milan,Mishra, Anju,Kundu, Sabuj
p. 100532 - 100545
(2016/11/09)

Hydrogenation of nitroarenes with palladium nanoparticles stabilized by alkyne derivatives in homogeneous phase
Palladium nanoparticles stabilized by alkyne derivatives catalyzed the hydrogenation of nitroarenes to the aryl amines in homogeneous phase. The reaction of nitrobenzene proceeded smoothly with a substrate-to-palladium molar ratio (S/Pd) of 51,000 under 8 atm of H2. The reaction under 1 atm of H2 with an S/Pd of 1030 was completed in 4 h. A series of substituted nitroarenes, including 4-acetyl- and 4-formylnitrobenzenes, were converted to the aryl amines with high chemoselectivity.
Arai, Noriyoshi,Onodera, Nozomi,Dekita, Atsushi,Hori, Junichi,Ohkuma, Takeshi
supporting information
p. 3913 - 3915
(2015/06/08)

Magnetically separable core-shell iron oxide@nickel nanoparticles as high-performance recyclable catalysts for chemoselective reduction of nitroaromatics
A magnetically separable core-shell iron oxide@nickel (IO@Ni) nanocatalyst was synthesized by reduction of Ni2+ ions in the presence of iron oxide (Fe2+, Fe3+) by a simple one-pot synthetic route using NaBH4 as a reducing agent and starch as a capping agent. The synthesized nanoparticles (NPs) were characterized by several techniques such as X-ray diffraction (XRD), high resolution transmission electron microscopy (HR-TEM), selected area electron diffraction (SAED), and energy dispersive X-ray spectroscopy (EDS). The core-shell iron oxide@nickel nanoparticles (IO@NiNPs) were found to have excellent activity for the hydrogenation reactions of aromatic nitro compounds under mild conditions using water as a green solvent. Excellent chemoselectivity and recyclability up to 30 cycles for the nitro group reduction was demonstrated.
Rathore, Puran Singh,Patidar, Rajesh,Shripathi,Thakore, Sonal
p. 286 - 295
(2015/02/02)

Iridium-catalyzed transfer hydrogenation of nitroarenes to anilines
A simple and general homogeneous catalyst system composed of commercially available [Ir(cod)Cl]2 and 1,10-phenanthroline has been developed for the selective transfer hydrogenation of nitroarenes to anilines. It utilized the readily accessible 2-propanol as a hydrogen donor and had wide substrate scope. A careful mechanistic investigation through real-time detection and a series of controlled experiments with possible intermediates was also carried out, which showed that the transformation proceeds via both phenylhydroxylamine and azobenzene intermediates and the reduction of hydrazobenzene leading to aniline might be the rate-determining step.
Chen, Shujie,Lu, Guoping,Cai, Chun
p. 5360 - 5365
(2015/07/07)

Gold-Catalyzed Reductive Transformation of Nitro Compounds Using Formic Acid: Mild, Efficient, and Versatile
Developing new efficient catalytic systems to convert abundant and renewable feedstocks into valuable products in a compact, flexible, and target-specific manner is of high importance in modern synthetic chemistry. Here, we describe a versatile set of mild catalytic conditions utilizing a single gold-based solid catalyst that enables the direct and additive-free preparation of four distinct and important amine derivatives (amines, formamides, benzimidazoles, and dimethlyated amines) from readily available formic acid (FA) and nitro starting materials with high level of chemoselectivity. By controlling the stoichiometry of the employed FA, which has attracted considerable interest in the area of sustainable chemistry because of its potential as an entirely renewable hydrogen carrier and as a versatile C1 source, a facile atom- and step-efficient transformation of nitro compounds can be realized in a modular fashion. Renewable formic acid as a flexible feedstock: A versatile heterogeneous gold-based catalytic system has been developed for the controlled, flexible, and target-specific reductive transformation of nitro compounds using stoichiometric equivalents of formic acid as a key starting material under mild and convenient conditions. The overall operational simplicity, high chemoselectivity, functional-group tolerance, and reusability of the catalyst make this approach an attractive and reliable tool for organic and process chemists.
Yu, Lei,Zhang, Qi,Li, Shu-Shuang,Huang, Jun,Liu, Yong-Mei,He, He-Yong,Cao, Yong
p. 3029 - 3035
(2015/09/28)

General transfer hydrogenation by activating ammonia-borane over cobalt nanoparticles
Cobalt nanoparticles containing both Co2+ and Co0 species supported on carbon nitride can function as heterogeneous nanocatalysts for a general transfer hydrogenation reaction in aqueous ammonia-borane solution at room temperature. The conversions of nitroarenes, olefins, imines, aldehydes, ketones and cyanobenzene are high with superior selectivity under mild conditions. This noble-metal-free catalyst is also cheap and reusable.
Zhao, Tian-Jian,Zhang, Ya-Nan,Wang, Kai-Xue,Su, Juan,Wei, Xiao,Li, Xin-Hao
p. 102736 - 102740
(2015/12/11)

Assembly of Primary (Hetero)Arylamines via CuI/Oxalic Diamide-Catalyzed Coupling of Aryl Chlorides and Ammonia
A general and practical catalytic system for aryl amination of aryl chlorides with aqueous or gaseous ammonia has been developed, with CuI as the catalyst and bisaryl oxalic diamides as the ligands. The reaction proceeds at 105-120°C to provide a diverse set of primary (hetero)aryl amines in high yields with various functional groups.
Fan, Mengyang,Zhou, Wei,Jiang, Yongwen,Ma, Dawei
supporting information
p. 5934 - 5937
(2015/12/11)

Nickel-catalyzed monoarylation of ammonia
Structurally diverse (hetero)aryl chloride, bromide, and tosylate electrophiles were employed in the Ni-catalyzed monoarylation of ammonia, including chemoselective transformations. The employed JosiPhos/[Ni(cod)2] catalyst system enables the use of commercially available stock solutions of ammonia, or the use of ammonia gas in these reactions, thereby demonstrating the versatility and potential scalability of the reported protocol. Proof-of-principle experiments established that air-stable [(JosiPhos)NiCl2] precatalysts can be employed successfully in such transformations. Lighten Up: The substrate scope of the title reaction includes (hetero)aryl chloride, bromide, and tosylate electrophiles. The versatility and potential scalability of the reported method is demonstrated by the use of either commercially available stock solutions of ammonia or ammonia gas.
Borzenko, Andrey,Rotta-Loria, Nicolas L.,Macqueen, Preston M.,Lavoie, Christopher M.,McDonald, Robert,Stradiotto, Mark
supporting information
p. 3773 - 3777
(2015/03/18)