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Polarographic and Cyclic Voltametric Reduction of p-Chlorobenzaldehyde Isonicotinoylhydrazone
p-Chlorobenzaldehyde isonicotinoylhydrazone (p-Cl-BAINH) exhibits a single wave in acid buffered solutions (pH 2-6) and two waves in alkaline buffered solutions (pH 7- 9).However, the compound exhibits three cathodic peaks in acid solution and two cathodic peaks in alkaline solutions.The electrode reactions are attributed to the reductive cleavage of =N-N- linkage and the reduction of the amide formed in the cleavage.
Reddy, Papammagari Raveendra,Rao, Sukuru Brahmaji
p. 1397 - 1398
(1988)
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Synthesis and characterization of copper nanoparticles on walnut shell for catalytic reduction and C-C coupling reaction
Walnut shell-stabilized copper nanoparticles (CuNP/WS) were successfully prepared by a simple reaction of copper sulfate and Sodium borohydride. Formation of copper nanoparticles in this bio-nanocomposite was observed by transmission electron microscopy (TEM) and energy dispersive X-ray spectroscope (EDX). CuNP/WS was found to be an efficient, inexpensive, easy to prepare, green and reusable catalyst in the reduction of aromatic nitro and nitrile compounds to their corresponding amines with NaBH4 at 35 °C in aqueous medium. We continued our studies on the application of this nanocomposite in the classic Ullman reaction to synthesize biaryl. This method has the advantages of high yields, elimination of expensive stabilizer and homogeneous catalysts, simple methodology and easy work up. The catalyst can be recovered from the reaction mixture and reused several times without any significant loss of catalytic activity.
Zamani, Asghar,Poursattar Marjani, Ahmad,Nikoo, Abbas,Heidarpour, Mojtaba,Dehghan, Ahmad
p. 176 - 181
(2018)
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Stable and Inert Cobalt Catalysts for Highly Selective and Practical Hydrogenation of C≡N and C=O Bonds
Novel heterogeneous cobalt-based catalysts have been prepared by pyrolysis of cobalt complexes with nitrogen ligands on different inorganic supports. The activity and selectivity of the resulting materials in the hydrogenation of nitriles and carbonyl compounds is strongly influenced by the modification of the support and the nitrogen-containing ligand. The optimal catalyst system ([Co(OAc)2/Phenα-Al2O3]-800 = Cat. E) allows for efficient reduction of both aromatic and aliphatic nitriles including industrially relevant dinitriles to primary amines under mild conditions. The generality and practicability of this system is further demonstrated in the hydrogenation of diverse aliphatic, aromatic, and heterocyclic ketones as well as aldehydes, which are readily reduced to the corresponding alcohols.
Chen, Feng,Topf, Christoph,Radnik, J?rg,Kreyenschulte, Carsten,Lund, Henrik,Schneider, Matthias,Surkus, Annette-Enrica,He, Lin,Junge, Kathrin,Beller, Matthias
p. 8781 - 8788
(2016)
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Hydrogenation of Aliphatic and Aromatic Nitriles Using a Defined Ruthenium PNP Pincer Catalyst
Selective catalytic reductions of nitriles are presented using the commercially available Ru-Macho-BH complex. A variety of aliphatic, aromatic and (hetero)cyclic nitriles including industrially important adipodinitrile are hydrogenated to the corresponding primary amines. Modelling suggests the reaction follows an outer sphere hydrogenation mechanism. An efficient and selective catalytic reduction of nitriles is presented using the commercially available Ru-Macho-BH complex. A variety of aliphatic, aromatic and (hetero)cyclic nitriles including the industrially important adipodinitrile are hydrogenated to the corresponding primary amines. The reaction follows an outer-sphere mechanism.
Neumann, Jacob,Bornschein, Christoph,Jiao, Haijun,Junge, Kathrin,Beller, Matthias
p. 5944 - 5948
(2015)
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Reaction of Diisobutylaluminum Borohydride, a Binary Hydride, with Selected Organic Compounds Containing Representative Functional Groups
The binary hydride, diisobutylaluminum borohydride [(iBu)2AlBH4], synthesized from diisobutylaluminum hydride (DIBAL) and borane dimethyl sulfide (BMS) has shown great potential in reducing a variety of organic functional groups. This unique binary hydride, (iBu)2AlBH4, is readily synthesized, versatile, and simple to use. Aldehydes, ketones, esters, and epoxides are reduced very fast to the corresponding alcohols in essentially quantitative yields. This binary hydride can reduce tertiary amides rapidly to the corresponding amines at 25 °C in an efficient manner. Furthermore, nitriles are converted into the corresponding amines in essentially quantitative yields. These reactions occur under ambient conditions and are completed in an hour or less. The reduction products are isolated through a simple acid-base extraction and without the use of column chromatography. Further investigation showed that (iBu)2AlBH4 has the potential to be a selective hydride donor as shown through a series of competitive reactions. Similarities and differences between (iBu)2AlBH4, DIBAL, and BMS are discussed.
Amberchan, Gabriella,Snelling, Rachel A.,Moya, Enrique,Landi, Madison,Lutz, Kyle,Gatihi, Roxanne,Singaram, Bakthan
supporting information
p. 6207 - 6227
(2021/05/06)

Generation of Oxidoreductases with Dual Alcohol Dehydrogenase and Amine Dehydrogenase Activity
The l-lysine-?-dehydrogenase (LysEDH) from Geobacillus stearothermophilus naturally catalyzes the oxidative deamination of the ?-amino group of l-lysine. We previously engineered this enzyme to create amine dehydrogenase (AmDH) variants that possess a new hydrophobic cavity in their active site such that aromatic ketones can bind and be converted into α-chiral amines with excellent enantioselectivity. We also recently observed that LysEDH was capable of reducing aromatic aldehydes into primary alcohols. Herein, we harnessed the promiscuous alcohol dehydrogenase (ADH) activity of LysEDH to create new variants that exhibited enhanced catalytic activity for the reduction of substituted benzaldehydes and arylaliphatic aldehydes to primary alcohols. Notably, these novel engineered dehydrogenases also catalyzed the reductive amination of a variety of aldehydes and ketones with excellent enantioselectivity, thus exhibiting a dual AmDH/ADH activity. We envisioned that the catalytic bi-functionality of these enzymes could be applied for the direct conversion of alcohols into amines. As a proof-of-principle, we performed an unprecedented one-pot “hydrogen-borrowing” cascade to convert benzyl alcohol to benzylamine using a single enzyme. Conducting the same biocatalytic cascade in the presence of cofactor recycling enzymes (i.e., NADH-oxidase and formate dehydrogenase) increased the reaction yields. In summary, this work provides the first examples of enzymes showing “alcohol aminase” activity.
Tseliou, Vasilis,Schilder, Don,Masman, Marcelo F.,Knaus, Tanja,Mutti, Francesco G.
supporting information
p. 3315 - 3325
(2020/12/11)

Comparative account of catalytic activity of Ru- and Ni-based nanocomposites towards reductive amination of biomass derived molecules
This work includes an effective comparison of metallic ruthenium and nickel nanoparticles loaded on montmorillonite clay (MMT) for reductive amination reaction of biomass-derived molecules. It comprises an eco-friendly reaction using water as a solvent, utilizing molecular hydrogen and liquor ammonia (25% aq. solution) for the synthesis of primary amines from bio-derived aldehydes within 3–10 h of reaction time. Various parameters such as temperature, hydrogen pressure, substrate/ammonia concentration ratio, and reaction time were optimized while comparing the selectivity of primary amines for both catalysts. The applicability scope of these catalysts was explored with a library of aryl and heterocyclic aldehydes. The reductive amination of crude furfural extracted from biomass feedstock (rice husk) and pure xylose sugar was tested, showing yields in the range of 11–36%, to show the wider industrial scope of both nanocomposites. Gram scale conversion was also carried out to showcase the bulk scalability of the Ru/MMT catalyst.
Bhanage, Bhalchandra M.,Gokhale, Tejas A.,Raut, Amol B.
(2021/06/18)

Simplified preparation of a graphene-co-shelled Ni/NiO@C nano-catalyst and its application in theN-dimethylation synthesis of amines under mild conditions
The development of Earth-abundant, reusable and non-toxic heterogeneous catalysts to be applied in the pharmaceutical industry for bio-active relevant compound synthesis remains an important goal of general chemical research.N-methylated compounds, as one of the most essential bioactive compounds, have been widely used in the fine and bulk chemical industries for the production of high-value chemicals. Herein, an environmentally friendly and simplified method for the preparation of graphene encapsulated Ni/NiO nanoalloy catalysts (Ni/NiO@C) was developed for the first time, for the highly selective synthesis ofN-methylated compounds using various functional amines and aldehydes under easy to handle, and industrially applicable conditions. A large number of primary and secondary amines (more than 70 examples) could be converted to the correspondingN,N-dimethylamines with the participation of different functional aldehydes, with an average yield of over 95%. A gram-scale synthesis also demonstrated a similar yield when compared with the benchmark test. In addition, it was further proved that the catalyst could easily be recycled because of its intrinsic magnetism and reused up to 10 times without losing its activity and selectivity. Also, for the first time, the tandem synthesis ofN,N-dimethylamine products in a one-pot process, using only a single earth-abundant metal catalyst, whose activity and selectivity were more than 99% and 94%, respectively, for all tested substrates, was developed. Overall, the advantages of this newly developed method include operational simplicity, high stability, easy recyclability, cost-effectiveness of the catalyst, and good functional group compatibility for the synthesis ofN-methylation products as well as the industrially applicable tandem synthesis process.
Liu, Jianguo,Ma, Longlong,Song, Yanpei,Zhang, Mingyue,Zhuang, Xiuzheng
supporting information
p. 4604 - 4617
(2021/06/30)

Self-regulated catalysis for the selective synthesis of primary amines from carbonyl compounds
Most current processes for the general synthesis of primary amines by reductive amination are performed with enormously excessive amounts of hazardous ammonia. It remains unclear how catalysts should be designed to regulate amination reaction dynamics at a low ammonia-to-substrate ratio for the quantitative synthesis of primary amines from the corresponding carbonyl compounds. Herein we show a facile control of the reaction selectivity in the layered boron nitride supported ruthenium catalyzed reductive amination reaction. Specifically, locating ruthenium to the edge surface of layered boron nitride leads to an increased hydrogenation activity owing to the enhanced interfacial electronic effects between ruthenium and the edge surface of boron nitride. This enables self-accelerated reductive amination reactions which quantitatively synthesize structurally diverse primary amines by reductive amination of carbonyl compounds with twofold ammonia. This journal is
Fan, Xiaomeng,Gao, Jin,Gao, Mingxia,Jia, Xiuquan,Ma, Jiping,Xu, Jie
supporting information
p. 7115 - 7121
(2021/09/28)

Selective Synthesis of Symmetrical Secondary Amines from Nitriles with a Pt?CuFe/Fe3O4 Catalyst and Ammonia Borane as Hydrogen Donor
Hydrogenation of nitriles is an efficient and environmentally friendly route to synthesize symmetrical secondary amines, but it usually produces a mixture of amines, imines, and hydrogenolysis by-products. Herein we report a magnetic quaternary-component Pt?CuFe/Fe3O4 nanocatalyst system for the selective synthesis of symmetrical secondary amines with ammonia borane as hydrogen donor. The catalyst with a low Pt loading (0.456 wt%) is the source of the activity, and the d-band electron transfer from Cu to Fe enhances the selectivity. This synergistic effect results in the transformation of benzonitrile to dibenzylamine with excellent conversion (up to 99 %) and nearly quantitative selectivity (up to 96 %) under mild reaction conditions, nevertheless, the reaction TOF is as high as up to 1409.9 h?1. A variety of nitriles are suitable for the synthesis of symmetrical secondary amines. More importantly, unwanted hydrogenolysis byproducts, especially toluene, is not detected at all. In addition, the catalyst is magnetically recoverable, and it can be reused up to five times.
Ai, Yongjian,Guo, Rongxiu,He, GuangQi,Hu, Ze-nan,Liang, Qionglin,Liu, Lei,Niu, Dun,Sun, Hong-bin,Tian, Haimeng,Zhang, Xinyue
p. 1783 - 1788
(2020/09/02)

A State-of-the-Art Heterogeneous Catalyst for Efficient and General Nitrile Hydrogenation
Cobalt-doped hybrid materials consisting of metal oxides and carbon derived from chitin were prepared, characterized and tested for industrially relevant nitrile hydrogenations. The optimal catalyst supported onto MgO showed, after pyrolysis at 700 °C, magnesium oxide nanocubes decorated with carbon-enveloped Co nanoparticles. This special structure allows for the selective hydrogenation of diverse and demanding nitriles to the corresponding primary amines under mild conditions (e.g. 70 °C, 20 bar H2). The advantage of this novel catalytic material is showcased for industrially important substrates, including adipodinitrile, picolinonitrile, and fatty acid nitriles. Notably, the developed system outperformed all other tested commercial catalysts, for example, Raney Nickel and even noble-metal-based systems in these transformations.
Formenti, Dario,Mocci, Rita,Atia, Hanan,Dastgir, Sarim,Anwar, Muhammad,Bachmann, Stephan,Scalone, Michelangelo,Junge, Kathrin,Beller, Matthias
supporting information
p. 15589 - 15595
(2020/10/02)

PROCESS FOR PREPARATION OF HALOGENATED BENZYLAMINE AND INTERMEDIATES THEROF
The present invention provides an improved process for the preparation of halogenated benzylamine having the formula I from halogenated benzonitriles, Formula I wherein, X1 is selected from group consisting of hydrogen, chloro or fluoro, provided atleast one X1 is chloro or fluoro.
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Page/Page column 19-20

(2020/08/13)

Nitrile Synthesis by Aerobic Oxidation of Primary Amines and in situ Generated Imines from Aldehydes and Ammonium Salt with Grubbs Catalyst
Herein, a Grubbs-catalyzed route for the synthesis of nitriles via the aerobic oxidation of primary amines is reported. This reaction accommodates a variety of substrates, including simple primary amines, sterically hindered β,β-disubstituted amines, allylamine, benzylamines, and α-amino esters. Reaction compatibility with various functionalities is also noted, particularly with alkenes, alkynes, halogens, esters, silyl ethers, and free hydroxyl groups. The nitriles were also synthesized via the oxidation of imines generated from aldehydes and NH4OAc in situ. (Figure presented.).
Utsumi, Tatsuki,Noda, Kenta,Kawauchi, Daichi,Ueda, Hirofumi,Tokuyama, Hidetoshi
supporting information
p. 3583 - 3588
(2020/08/05)

Method for preparing benzylamine compound by using halogenated hydrocarbon and liquid ammonia (by machine translation)
The method comprises the following steps: under an inert atmosphere, continuously stirring, slowly adding halogenated hydrocarbon to liquid ammonia after passing through an aprotic inert solvent, reacting to obtain the corresponding benzylamine compound, and adding a protonic alkaline substance into the liquid ammonia prior to the addition of the halogenated hydrocarbon. The method has the characteristics of mild reaction conditions, environmental friendliness, safe and convenient operation, high yield, less three wastes, suitability for industrialization and the like. (by machine translation)
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Paragraph 00031-0045

(2020/08/09)

Facile synthesis of controllable graphene-co-shelled reusable Ni/NiO nanoparticles and their application in the synthesis of amines under mild conditions
The primary objective of many researchers in chemical synthesis is the development of recyclable and easily accessible catalysts. These catalysts should preferably be made from Earth-abundant metals and have the ability to be utilised in the synthesis of pharmaceutically important compounds. Amines are classified as privileged compounds, and are used extensively in the fine and bulk chemical industries, as well as in pharmaceutical and materials research. In many laboratories and in industry, transition metal catalysed reductive amination of carbonyl compounds is performed using predominantly ammonia and H2. However, these reactions usually require precious metal-based catalysts or RANEY nickel, and require harsh reaction conditions and yield low selectivity for the desired products. Herein, we describe a simple and environmentally friendly method for the preparation of thin graphene spheres that encapsulate uniform Ni/NiO nanoalloy catalysts (Ni/NiO?C) using nickel citrate as the precursor. The resulting catalysts are stable and reusable and were successfully used for the synthesis of primary, secondary, tertiary, and N-methylamines (more than 62 examples). The reaction couples easily accessible carbonyl compounds (aldehydes and ketones) with ammonia, amines, and H2 under very mild industrially viable and scalable conditions (80 °C and 1 MPa H2 pressure, 4 h), offering cost-effective access to numerous functionalized, structurally diverse linear and branched benzylic, heterocyclic, and aliphatic amines including drugs and steroid derivatives. We have also demonstrated the scale-up of the heterogeneous amination protocol to gram-scale synthesis. Furthermore, the catalyst can be immobilized on a magnetic stirring bar and be conveniently recycled up to five times without any significant loss of catalytic activity and selectivity for the product.
Cui, Zhibing,Liu, Jianguo,Liu, Qiying,Ma, Longlong,Singh, Thishana,Wang, Chenguang,Wang, Nan,Zhu, Yuting
supporting information
p. 7387 - 7397
(2020/11/19)

Synthesis of oxalamides by acceptorless dehydrogenative coupling of ethylene glycol and amines and the reverse hydrogenation catalyzed by ruthenium
A sustainable, new synthesis of oxalamides, by acceptorless dehydrogenative coupling of ethylene glycol with amines, generating H2, homogeneously catalyzed by a ruthenium pincer complex, is presented. The reverse hydrogenation reaction is also accomplished using the same catalyst. A plausible reaction mechanism is proposed based on stoichiometric reactions, NMR studies, X-ray crystallography as well as observation of plausible intermediates.
Ben-David, Yehoshoa,Diskin-Posner, Yael,Milstein, David,Zhou, Quan-Quan,Zou, You-Quan
p. 7188 - 7193
(2020/07/23)

Manganese catalyzed selective hydrogenation of cyclic imides to diols and amines
Herein we report the selective hydrogenation of cyclic imides to diols and amines, homogeneously catalyzed for the first time by a complex of an earth-abundant metal, a manganese pincer complex. A plausible catalytic cycle is proposed based on informative mechanistic experiments.
Das, Uttam Kumar,Janes, Trevor,Kumar, Amit,Milstein, David
supporting information
p. 3079 - 3082
(2020/06/19)

Effects of ruthenium hydride species on primary amine synthesis by direct amination of alcohols over a heterogeneous Ru catalyst
Heterogeneously catalysed synthesis of primary amines by direct amination of alcohols with ammonia has long been an elusive goal. In contrast to reported Ru-based catalytic systems, we report that Ru-MgO/TiO2 acts as an effective heterogeneous catalyst for the direct amination of a variety of alcohols to primary amines at low temperatures of ca. 100 °C without the introduction of H2 gas. The present system could be applied to a variety of alcohols and provides an efficient synthetic route for 2,5-bis(aminomethyl)furan (BAMF), an attention-getting biomonomer. The high catalytic performance can be rationalized by the reactivity tuning of Ru-H species using MgO. Spectroscopic measurements suggest that MgO enhances the reactivity of hydride species by electron donation from MgO to Ru.
Hara, Michikazu,Kamata, Keigo,Kita, Yusuke,Kuwabara, Midori,Yamadera, Satoshi
p. 9884 - 9890
(2020/10/06)

Scope and limitations of reductive amination catalyzed by half-sandwich iridium complexes under mild reaction conditions
The conversion of aldehydes and ketones to 1° amines could be promoted by half-sandwich iridium complexes using ammonium formate as both the nitrogen and hydride source. To optimize this method for green chemical synthesis, we tested various carbonyl substrates in common polar solvents at physiological temperature (37 °C) and ambient pressure. We found that in methanol, excellent selectivity for the amine over alcohol/amide products could be achieved for a broad assortment of carbonyl-containing compounds. In aqueous media, selective reduction of carbonyls to 1° amines was achieved in the absence of acids. Unfortunately, at Ir catalyst concentrations of 1 mM in water, reductive amination efficiency dropped significantly, which suggest that this catalytic methodology might be not suitable for aqueous applications where very low catalyst concentration is required (e.g., inside living cells).
Nguyen, Dat P.,Sladek, Rudolph N.,Do, Loi H.
supporting information

(2020/07/15)

Ultra-small cobalt nanoparticles from molecularly-defined Co-salen complexes for catalytic synthesis of amines
We report the synthesis of in situ generated cobalt nanoparticles from molecularly defined complexes as efficient and selective catalysts for reductive amination reactions. In the presence of ammonia and hydrogen, cobalt-salen complexes such as cobalt(ii)-N,N′-bis(salicylidene)-1,2-phenylenediamine produce ultra-small (2-4 nm) cobalt-nanoparticles embedded in a carbon-nitrogen framework. The resulting materials constitute stable, reusable and magnetically separable catalysts, which enable the synthesis of linear and branched benzylic, heterocyclic and aliphatic primary amines from carbonyl compounds and ammonia. The isolated nanoparticles also represent excellent catalysts for the synthesis of primary, secondary as well as tertiary amines including biologically relevant N-methyl amines.
Beller, Matthias,Chandrashekhar, Vishwas G.,Gawande, Manoj B.,Jagadeesh, Rajenahally V.,Kalevaru, Narayana V.,Kamer, Paul C. J.,Senthamarai, Thirusangumurugan,Zbo?il, Radek
p. 2973 - 2981
(2020/03/27)

Ambient-Temperature Synthesis of Primary Amines via Reductive Amination of Carbonyl Compounds
Efficient synthesis of primary amines via low-temperature reductive amination of carbonyl compounds using NH3 and H2 as the nitrogen and hydrogen resources is highly desired and challenging in the chemistry community. Herein, we employed naturally occurring phytic acid as a renewable precursor to fabricate titanium phosphate (TiP)-supported Ru nanocatalysts with different reduction degrees of RuO2 (Ru/TiP-x, x represents the reduction temperature) by combining ball milling and molten-salt processes. Very interestingly, the obtained Ru/TiP-100 had good catalytic performance for the reductive amination of carbonyl compounds at ambient temperature, resulting from the synergistic cooperation of the support (TiP) and the Ru/RuO2 with a suitable proportion of Ru0 (52%). Various carbonyl compounds could be efficiently converted into the corresponding primary amines with high yields. More importantly, the conversion of other substrates with reducible groups could also be achieved at ambient temperature. Detailed investigations indicated that the partially reduced Ru and the support (TiP) were indispensable. The high activity and selectivity of Ru/TiP-100 catalyst originates from the relatively high acidity and the suitable electron density of metallic Ru0.
Xie, Chao,Song, Jinliang,Hua, Manli,Hu, Yue,Huang, Xin,Wu, Haoran,Yang, Guanying,Han, Buxing
p. 7763 - 7772
(2020/08/21)

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)

The Synthesis of Primary Amines through Reductive Amination Employing an Iron Catalyst
The reductive amination of ketones and aldehydes by ammonia is a highly attractive method for the synthesis of primary amines. The use of catalysts, especially reusable catalysts, based on earth-abundant metals is similarly appealing. Here, the iron-catalyzed synthesis of primary amines through reductive amination was realized. A broad scope and a very good tolerance of functional groups were observed. Ketones, including purely aliphatic ones, aryl–alkyl, dialkyl, and heterocyclic, as well as aldehydes could be converted smoothly into their corresponding primary amines. In addition, the amination of pharmaceuticals, bioactive compounds, and natural products was demonstrated. Many functional groups, such as hydroxy, methoxy, dioxol, sulfonyl, and boronate ester substituents, were tolerated. The catalyst is easy to handle, selective, and reusable and ammonia dissolved in water could be employed as the nitrogen source. The key is the use of a specific Fe complex for the catalyst synthesis and an N-doped SiC material as catalyst support.
B?umler, Christoph,Bauer, Christof,Kempe, Rhett
p. 3110 - 3114
(2020/06/01)

PROCESS FOR PRODUCING AN AMINE IN A SOLVENT SYSTEM CONTAINING WATER
The present invention pertains to a process for producing an amine from an aldehyde or a precursor thereof, or a ketone in a solvent system containing water. The process is more environmentally friendly and permits to obtain an amine compound under mild reaction conditions.
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(2019/10/04)

Ruthenium(II)-cored supramolecular organic framework-mediated recyclable visible light photoreduction of azides to amines and cascade formation of lactams
Ru(bpy)3]2+-cored supramolecular organic framework SMOF-1, assembled from a [Ru(bpy)3]2+-derived hexaarmed molecule and cucurbit[8]uril, has been demonstrated to heterogeneously catalyze visible light-induced reduction of phenyl, benzyl, 2-phenylethyl and 3-phenylpropyl azides in acetonitrile to produce the corresponding amines in good to high yields. For the last two kinds of azides that bear a CO2Me group at the para-position of the benzene ring, cascade reactions take place to generate the corresponding lactams in high yields. Compared with homogeneous control [Ru(bpy)3]Cl2, SMOF-1 exhibits remarkably increased photocatalysis activity as a result of synergistic effect of the [Ru(bpy)3]2+ units that form cubic cages to host the azide molecules and related intermediates. Moreover, SMOF-1 displays high recyclability and considerable photocatalysis activity after 3 to 12 runs.
Wu, Yi-Peng,Yan, Meng,Gao, Zhong-Zheng,Hou, Jun-Li,Wang, Hui,Zhang, Dan-Wei,Zhang, Junliang,Li, Zhan-Ting
p. 1383 - 1386
(2019/05/06)

Cobalt pincer complexes for catalytic reduction of nitriles to primary amines
Various cobalt pincer type complexes 1-6 were applied for the catalytic hydrogenation of nitriles to amines. Among these, catalyst 4 is the most efficient, allowing the reduction of aromatic as well as aliphatic nitriles in moderate to excellent yields.
Schneek?nig, Jacob,Tannert, Bianca,Hornke, Helen,Beller, Matthias,Junge, Kathrin
p. 1779 - 1783
(2019/04/27)

A ppm level Rh-based composite as an ecofriendly catalyst for transfer hydrogenation of nitriles: Triple guarantee of selectivity for primary amines
Hydrogenation of nitriles to afford amines under mild conditions is a challenging task with an inexpensive heterogeneous catalyst, and it is even more difficult to obtain primary amines selectively because of the accompanying self-coupling side reactions. An efficient catalytic system was designed as Fe3O4@nSiO2-NH2-RhCu@mSiO2 to prepare primary amines through the transfer hydrogenation of nitrile compounds with economical HCOOH as the hydrogen donor. The loading of rhodium in the catalyst could be at the ppm level, and the TOF reaches 6803 h-1 for Rh. This catalytic system has a wide substrate range including some nitriles that could not proceed in the previous literature. The experimental results demonstrate that the excellent selectivity for primary amines is guaranteed by three tactics, which are the strong active site, the inhibition of side products by the hydrogen source and the special pore structure of the catalyst. In addition, the catalyst could be reused ten times without activity loss through convenient magnetic recovery.
Liu, Lei,Li, Jifan,Ai, Yongjian,Liu, Yuhong,Xiong, Jialiang,Wang, Hongdong,Qiao, Yijun,Liu, Wenrui,Tan, Shanchao,Feng, Shaofei,Wang, Kunpeng,Sun, Hongbin,Liang, Qionglin
p. 1390 - 1395
(2019/03/26)

Combining Photo-Organo Redox- and Enzyme Catalysis Facilitates Asymmetric C-H Bond Functionalization
In this study, we combined photo-organo redox catalysis and biocatalysis to achieve asymmetric C–H bond functionalization of simple alkane starting materials. The photo-organo catalyst anthraquinone sulfate (SAS) was employed to oxyfunctionalise alkanes to aldehydes and ketones. We coupled this light-driven reaction with asymmetric enzymatic functionalisations to yield chiral hydroxynitriles, amines, acyloins and α-chiral ketones with up to 99 % ee. In addition, we demonstrate functional group interconversion to alcohols, esters and carboxylic acids. The transformations can be performed as concurrent tandem reactions. We identified the degradation of substrates and inhibition of the biocatalysts as limiting factors affecting compatibility, due to reactive oxygen species generated in the photocatalytic step. These incompatibilities were addressed by reaction engineering, such as applying a two-phase system or temporal and spatial separation of the catalysts. Using a selection of eleven starting alkanes, one photo-organo catalyst and 8 diverse biocatalysts, we synthesized 26 products and report for the model compounds benzoin and mandelonitrile > 97 % ee at gram scale.
Zhang, Wuyuan,Fueyo, Elena Fernandez,Hollmann, Frank,Martin, Laura Leemans,Pesic, Milja,Wardenga, Rainer,H?hne, Matthias,Schmidt, Sandy
p. 80 - 84
(2019/01/04)

Nitrogen-Doped Carbon-Supported Nickel Nanoparticles: A Robust Catalyst to Bridge the Hydrogenation of Nitriles and the Reductive Amination of Carbonyl Compounds for the Synthesis of Primary Amines
An efficient method was developed for the synthesis of primary amines either from the hydrogenation of nitriles or reductive amination of carbonyl compounds. The reactions were catalyzed by nitrogen-doped mesoporous carbon (MC)-supported nickel nanoparticles (abbreviated as MC/Ni). The MC/Ni catalyst demonstrated high catalytic activity for the hydrogenation of nitriles into primary amines in high yields (81.9–99 %) under mild reaction conditions (80 °C and 2.5 bar H2). The MC/Ni catalyst also promoted the reductive amination of carbonyl compounds for the synthesis of primary amines at 80 °C and 1 bar H2. The hydrogenation of nitriles and the reductive amination proceeded through the same intermediates for the generation of the primary amines. To the best of our knowledge, no other heterogeneous non-noble metal catalysts have been reported for the synthesis of primary amines under mild conditions, both from the hydrogenation of nitriles and reductive amination.
Zhang, Yangmin,Yang, Hanmin,Chi, Quan,Zhang, Zehui
p. 1246 - 1255
(2019/03/07)

Nano-Fe3O4@SiO2-SO3H: A magnetic, reusable solid-acid catalyst for solvent-free reduction of oximes to amines with the NaBH3CN/ZrCl4 system
In this study, the immobilization of sulfonic acid on silica-layered magnetite was carried out by the reaction of ClSO3H with silica-layered magnetite. The prepared magnetic nanoparticles of Fe3O4@SiO2-SO3H were then characterized using scanning electron microscopy, energy dispersive X-ray spectroscopy, X-ray diffraction, Fourier transform infrared spectroscopy, vibrating sample magnetometry, and transmission electron microscopy. The sulfonated nanocomposite exhibited excellent catalytic activity and reusability in the reduction of various aldoximes and ketoximes with NaBH3CN in the presence of ZrCl4. All reactions were carried out under solvent-free conditions (r.t. or 75–80°C) within 3–70 min to afford amines in high to excellent yields.
Sadighnia, Leila,Zeynizadeh, Behzad,Karami, Shiva,Abdollahi, Mohammad
p. 535 - 542
(2019/01/04)

Manganese catalyzed hydrogenation of carbamates and urea derivatives
We report the hydrogenation of carbamates and urea derivatives, two of the most challenging carbonyl compounds to be hydrogenated, catalyzed for the first time by a complex of an earth-abundant metal. The hydrogenation reaction of these CO2-derived compounds, catalyzed by a manganese pincer complex, yields methanol in addition to amine and alcohol, which makes this methodology a sustainable alternative route for the conversion of CO2 to methanol, involving a base-metal catalyst. Moreover, the hydrogenation proceeds under mild pressure (20 bar). Our observations support a hydrogenation mechanism involving the Mn-H complex. A plausible catalytic cycle is proposed based on informative mechanistic experiments.
Das, Uttam Kumar,Kumar, Amit,Ben-David, Yehoshoa,Iron, Mark A.,Milstein, David
supporting information
p. 12962 - 12966
(2019/08/26)

Preparation of nitrogen-doped carbon supported cobalt catalysts and its application in the reductive amination
The use of non-noble metal catalysts with high activity is of great importance for organic transformations. Herein, nitrogen-doped carbon supported cobalt catalysts with high surface area up to 981.2 m2/g were prepared via the simple pyrolysis of cobalt coordinated organic polymers with silica as the hard template. The pyrolysis temperature showed a great effect on the structure and properties of the as-prepared catalysts. The Co@NC-800 catalyst with the pyrolysis temperature of 800 °C demonstrated a high activity for the selective reductive amination of carbonyl compounds to primary amines with ammonia and hydrogen. Structurally-diverse primary amines with yields in the range from 81.8% to 100% were attained under the optimal conditions. The Co@NC-800 catalyst could be reused without the loss of its activity. The Co@NC-800 catalyst demonstrated comparable activity as the reported heterogeneous noble metal catalysts.
Yuan, Ziliang,Liu, Bing,Zhou, Peng,Zhang, Zehui,Chi, Quan
p. 347 - 356
(2019/01/24)

Reusable Nickel Nanoparticles-Catalyzed Reductive Amination for Selective Synthesis of Primary Amines
The preparation of nickel nanoparticles as efficient reductive amination catalysts by pyrolysis of in situ generated Ni-tartaric acid complex on silica is presented. The resulting stable and reusable Ni-nanocatalyst enables the synthesis of functionalized and structurally diverse primary benzylic, heterocyclic and aliphatic amines starting from inexpensive and readily available carbonyl compounds and ammonia in presence of molecular hydrogen. Applying this Ni-based amination protocol, -NH2 moiety can be introduced in structurally complex compounds, for example, steroid derivatives and pharmaceuticals.
Murugesan, Kathiravan,Beller, Matthias,Jagadeesh, Rajenahally V.
supporting information
p. 5064 - 5068
(2019/03/19)

Cobalt complex, preparation method thereof, and application thereof in selective catalysis of transfer hydrogenation reaction of cyano group
The invention discloses a cobalt complex, a preparation method thereof, and an application thereof in the selective catalysis of a transfer hydrogenation reaction of a cyano group. The structural formula of the cobalt complex is represented by formula I. The cobalt complex is prepared through a reaction of a cobalt salt and an NNP ligand or a PNP ligand under the protection of an inert atmosphere;and the chemical formula of the cobalt salt is CoX12, wherein X1 represents halogen, a sulfate radical, a perchlorate radical, a hexafluorophosphate radical, a hexafluoroantimonate radical, a tetrafluoroborate radical, a trifluoromethanesulfonate radical or a tetra(pentafluorophenyl)borate radical. The cobalt complex can be used in the selective catalysis of the transfer hydrogenation reaction ofthe cyano group to obtain a primary amine compound, a secondary amine compound and a tertiary amine compound, the primary amine compound, the secondary amine compound and the tertiary amine compoundare important intermediates in a series of subsequent functionalizing reactions, and the cobalt complex has a very high catalysis activity, and has great research values and a great application prospect.
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Paragraph 0157-0159; 0161

(2018/05/07)

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

Synthesis of cobalt nanoparticles by pyrolysis of Vitamin B12: A non-noble-metal catalyst for efficient hydrogenation of nitriles
A facile preparation of vitamin B12-derived carbonaceous cobalt particles supported on ceria is reported. The resulting composite material is obtained upon wet impregnation of ceria with natural cyanocobalamin and consecutive pyrolysis under inert conditions. The novel catalyst shows good to excellent performance in the industrially relevant heterogeneous hydrogenation of nitriles to the corresponding primary amines.
Ferraccioli, Raffaella,Borovika, Diana,Surkus, Annette-Enrica,Kreyenschulte, Carsten,Topf, Christoph,Beller, Matthias
p. 499 - 507
(2018/02/07)

Bioproduction of benzylamine from renewable feedstocks via a nine-step artificial enzyme cascade and engineered metabolic pathways
Production of chemicals from renewable feedstocks has been an important task for sustainable chemical industry. Although microbial fermentation has been widely employed to produce many biochemicals, it is still very challenging to access non-natural chemicals. Two methods (biotransformation and fermentation) have been developed for the first bio-derived synthesis of benzylamine, a commodity non-natural amine with broad applications. Firstly, a nine-step artificial enzyme cascade was designed by biocatalytic retrosynthetic analysis and engineered in recombinant E. coli LZ243. Biotransformation of l-phenylalanine (60 mm) with the E. coli cells produced benzylamine (42 mm) in 70 % conversion. Importantly, the cascade biotransformation was scaled up to 100 mL and benzylamine was successfully isolated in 57 % yield. Secondly, an artificial biosynthesis pathway to benzylamine from glucose was developed by combining the nine-step cascade with an enhanced l-phenylalanine synthesis pathway in cells. Fermentation with E. coli LZ249 gave benzylamine in 4.3 mm concentration from glucose. In addition, one-pot syntheses of several useful benzylamines from the easily available styrenes were achieved, representing a new type of alkene transformation by formal oxidative cleavage and reductive amination.
Zhou, Yi,Wu, Shuke,Mao, Jiwei,Li, Zhi
p. 2221 - 2228
(2018/10/20)

Selective synthesis of mono- and di-methylated amines using methanol and sodium azide as C1 and N1 sources
A Ru(ii) complex mediated synthesis of various N,N-dimethyl and N-monomethyl amines from organic azides using methanol as a methylating agent is reported. This methodology was successfully applied for a one-pot reaction of bromide derivatives and sodium azide in methanol. Notably, by controlling the reaction time several N-monomethylated and N,N-dimethylated amines were synthesized selectively. The practical applicability of this tandem process was revealed by preparative scale reactions with different organic azides and synthesis of an anti-vertigo drug betahistine. Several kinetic experiments and DFT studies were carried out to understand the mechanism of this transformation.
Chakrabarti, Kaushik,Mishra, Anju,Panja, Dibyajyoti,Paul, Bhaskar,Kundu, Sabuj
supporting information
p. 3339 - 3345
(2018/07/29)

Selective Hydrogenation of Cyclic Imides to Diols and Amines and Its Application in the Development of a Liquid Organic Hydrogen Carrier
Direct hydrogenation of a broad variety of cyclic imides to diols and amines using a ruthenium catalyst is reported here. We have applied this strategy toward the development of a new liquid organic hydrogen carrier system based on the hydrogenation of bis-cyclic imide that is formed by the dehydrogenative coupling of 1,4-butanediol and ethylenediamine using a new ruthenium catalyst. The rechargeable system has a maximum gravimetric hydrogen storage capacity of 6.66 wt%.
Kumar, Amit,Janes, Trevor,Espinosa-Jalapa, Noel Angel,Milstein, David
supporting information
p. 7453 - 7457
(2018/06/08)

N-Alkylation of Aqueous Ammonia with Alcohols Leading to Primary Amines Catalyzed by Water-Soluble N-Heterocyclic Carbene Complexes of Iridium
A new catalytic system for the N-monoalkylation of aqueous ammonia with a variety of alcohols was developed. Water-soluble dicationic complexes of iridium bearing N-heterocyclic carbene and diammine ligands exhibited high catalytic activity for this type of reaction on the basis of hydrogen-transfer processes without generating harmful or wasteful byproducts. Various primary amines were efficiently synthesized by using safe, inexpensive, and easily handled aqueous ammonia as a nitrogen source. For example, the reaction of 1-(4-methylphenyl)ethanol with aqueous ammonia in the presence of a water-soluble N-heterocyclic carbene complex of iridium at 150 °C for 40 h gave 1-(4-methylphenyl)ethylamine in 83 % yield.
Fujita, Ken-Ichi,Furukawa, Shohichi,Morishima, Namino,Shimizu, Mineyuki,Yamaguchi, Ryohei
p. 1993 - 1997
(2018/03/13)

A high performance catalyst of shape-specific ruthenium nanoparticles for production of primary amines by reductive amination of carbonyl compounds
The creation of metal catalysts with highly active surfaces is pivotal to meeting the strong economic demand of the chemical industry. Specific flat-shaped pristine fcc ruthenium nanoparticles having a large fraction of atomically active {111} facets exposed on their flat surfaces have been developed that act as a highly selective and reusable heterogeneous catalyst for the production of various primary amines at exceedingly high reaction rates by the low temperature reductive amination of carbonyl compounds. The high performance of the catalyst is attributed to the large fraction of metallic Ru serving as active sites with weak electron donating ability that prevail on the surface exposed {111} facets of flat-shaped fcc Ru nanoparticles. This catalyst exhibits a highest turnover frequency (TOF) of ca. 1850 h-1 for a model reductive amination of biomass derived furfural to furfurylamine and provides a reaction rate approximately six times higher than that of an efficient and selective support catalyst of Ru-deposited Nb2O5 (TOF: ca. 310 h-1).
Chandra, Debraj,Inoue, Yasunori,Sasase, Masato,Kitano, Masaaki,Bhaumik, Asim,Kamata, Keigo,Hosono, Hideo,Hara, Michikazu
p. 5949 - 5956
(2018/07/25)

Bifunctional N-Doped Co@C Catalysts for Base-Free Transfer Hydrogenations of Nitriles: Controllable Selectivity to Primary Amines vs Imines
The transfer hydrogenation of nitriles is an important and alternative strategy to produce primary amines or imines, both of which play a crucial role in the synthesis of fine chemicals and pharmaceuticals. Nevertheless, developing highly active bifunctional catalyst system with controllable selectivity for these reactions still remains a huge challenge. In this study, we presented a bifunctional N-doped Co@C catalyst system (Co@NC) for the selective transfer hydrogenation of nitriles into either primary amines or imines. The Co@NC was prepared by the direct pyrolysis of an N-containing Co-MOF under an inert atmosphere, where the N-containing ligands could be transformed into highly graphitic N-doped carbon, endowing the catalysts with high-density special basic sites, while the Co2+ ions were reduced to uniform Co nanoparticles which were dispersed on or embedded in N-doped graphitic structures. Under base-free conditions with isopropyl alcohol as both proton donor and solvent, the optimized Co@NC-900 (obtained at 900 °C) catalyst could convert nitriles into primary amines or imines at will with surprising selectivities (mostly higher than 90%), depending on the solvent volume added to the reaction systems. Furthermore, a possible reaction mechanism was proposed. The N-derived basic sites on Co@NC could play a role similar to that of the base additives, which not only inhibit the formation of polyamine or prevent the products stacked on the surface of catalysts but also effectively promote the transfer hydrogenation of nitriles. The generated corresponding primary imines could controllably attack the primary imine intermediates to form imines by adjusting the concentration of Co@NC. It is clear that this strategy offers a high-performance catalyst system for base-free transfer hydrogenations of nitriles to selectively produce primary amines vs imines.
Long, Jilan,Shen, Kui,Li, Yingwei
p. 275 - 284
(2017/06/07)

Versatile Dynamic Covalent Assemblies for Probing π-Stacking and Chirality Induction from Homotopic Faces
Herein we report for the first time the use of dynamic covalent reactions (DCRs) for building a π-stacking model system and further quantifying its substituent effects (SEs), which remain a topic of debate despite the rich history of stacking. A general DCR between 10-methylacridinium ion and primary amines was discovered, in which π-stacking played a stabilizing role. Facile quantification of SEs with in situ competing π-stacking systems was next achieved in the form of amine exchange exhibiting structural diversity by simply varying components. The linear correlation with σm in Hammett plots indicates the dominance of purely electrostatic SEs, and the additivity of SEs is in line with the direct interaction model. With α-chiral amines π-stacking within the adduct enabled chirality transfer from homotopic faces. The strategy of dynamic covalent assembly should be appealing to future research of probing weak interactions and manipulating chirality.
Ye, Hebo,Hai, Yu,Ren, Yulong,You, Lei
supporting information
p. 3804 - 3809
(2017/03/27)

Electronic Effect of Ruthenium Nanoparticles on Efficient Reductive Amination of Carbonyl Compounds
Highly selective synthesis of primary amines over heterogeneous catalysts is still a challenge for the chemical industry. Ruthenium nanoparticles supported on Nb2O5 act as a highly selective and reusable heterogeneous catalyst for the low-temperature reductive amination of various carbonyl compounds that contain reduction-sensitive functional groups such as heterocycles and halogens with NH3 and H2 and prevent the formation of secondary amines and undesired hydrogenated byproducts. The selective catalysis of these materials is likely attributable to the weak electron-donating capability of Ru particles on the Nb2O5 surface. The combination of this catalyst and homogeneous Ru systems was used to synthesize 2,5-bis(aminomethyl)furan, a monomer for aramid production, from 5-(hydroxymethyl)furfural without a complex mixture of imine byproducts.
Komanoya, Tasuku,Kinemura, Takashi,Kita, Yusuke,Kamata, Keigo,Hara, Michikazu
supporting information
p. 11493 - 11499
(2017/08/30)

MOF-derived cobalt nanoparticles catalyze a general synthesis of amines
The development of base metal catalysts for the synthesis of pharmaceutically relevant compounds remains an important goal of chemical research. Here, we report that cobalt nanoparticles encapsulated by a graphitic shell are broadly effective reductive amination catalysts. Their convenient and practical preparation entailed template assembly of cobaltdiamine- dicarboxylic acid metal organic frameworks on carbon and subsequent pyrolysis under inert atmosphere.The resulting stable and reusable catalysts were active for synthesis of primary, secondary, tertiary, and N-methylamines (more than 140 examples).The reaction couples easily accessible carbonyl compounds (aldehydes and ketones) with ammonia, amines, or nitro compounds, and molecular hydrogen under industrially viable and scalable conditions, offering cost-effective access to numerous amines, amino acid derivatives, and more complex drug targets.
Jagadeesh, Rajenahally V.,Murugesan, Kathiravan,Alshammari, Ahmad S.,Neumann, Helfried,Pohl, Marga-Martina,Radnik, J?rg,Beller, Matthias
p. 326 - 332
(2017/09/28)

Ligand, metal complex containing ligand, and reaction using metal complex containing ligand
A hydrogen transfer reaction may be more efficiently promoted by using a metal complex represented by Formula (2): (wherein, R1 to R8 are the same or different, and each represents a hydrogen atom, a substituted or unsubstituted alkyl group or the like; or wherein; R1 and R2, R2 and R3, R3 and R4, R4 and R5, and R5 and R6 are respectively bonded to each other to form a bivalent hydrocarbon group; R9 are the same or different, and each represents an alkyl group or cycloalkyl group; M is ruthenium (Ru) or the like; X is a ligand; and n is 0, 1 or 2). More specifically, the metal complex enables a hydrogenation reaction of various substrates having a stable carbonyl group or the like to be advanced with a high yield under mild conditions.
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Page/Page column 46-50

(2016/10/31)

A method for the production of primary amines
The invention relates to the field of chemical industry and particularly relates to a method for preparing primary amine by using the raw materials including halogenated hydrocarbon (or hydrocarbon alcohol sulfonate) and ammonia water (or formamide). The method comprises the following three steps: (1) imidization: 3,4-diarylfuran-2,5-diketone (I) reacts with ammonia (or formamide) and the like to obtain 3,4-diaryl-1H-pyrrole-2,5-diketone (II); (2) N-hydrocarbylation: 3,4-diaryl-1H-pyrrole-2,5-diketone (II) generates an N-hydrocarbylation reaction with halogenated hydrocarbon (or hydrocarbon alcohol sulfonate) in the presence of alkali to obtain N-hydrocarbyl-3,4-diaryl-1H-pyrrole-2,5-diketone (III); and (3) hydrolysis: N-hydrocarbyl-3,4-diaryl-1H-pyrrole-2,5-diketone (III) is subjected to alkali hydrolysis to obtain primary amine and the generated 2,3-diaryl maleate is subjected to acid treatment and automatic ring closing to form 3,4-diaryl furan-2,5-diketone (I) which is subjected to imidization and directly applied to the N-hydrocarbylation reaction. The method provided by the invention has the characteristics that the 3,4-diaryl furan-2,5-diketone can be circularly used at a high recovery rate, the molar ratio of the raw materials is low, and the yield of the product primary amine is high.
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Paragraph 0237; 0247

(2016/10/09)

Efficient chemoselective hydrogenation of organic azides catalyzed by palladium nanoparticles with alkyne-derived homogeneous supports
Catalytic chemoselective hydrogenation of organic azides using palladium nanoparticles stabilized by alkyne derivatives was studied. A broad range of aromatic and aliphatic azides were smoothly reduced to the corresponding amines in excellent yields with a quite small amount of the catalyst. Hydrogenation of 3-phenylpropylazide gave 3-phenylpropylamine almost quantitatively with a substrate-to-palladium molar ratio (S/Pd) of 12,900 under 8?atm of H2. The reaction under 1?atm of H2also proceeded smoothly with an S/Pd of 1000. Several reduction-sensitive functional groups, such as carbonyl, halide, benzylic OH, and aliphatic nitro were well tolerated under the reaction conditions.
Arai, Noriyoshi,Onodera, Nozomi,Ohkuma, Takeshi
supporting information
p. 4183 - 4186
(2016/08/24)

NNP-Type Pincer Imidazolylphosphine Ruthenium Complexes: Efficient Base-Free Hydrogenation of Aromatic and Aliphatic Nitriles under Mild Conditions
A series of seven novel NImNHP-type pincer imidazolylphosphine ruthenium complexes has been synthesized and fully characterized. The use of hydrogenation of benzonitrile as a benchmark test identified [RuHCl(CO)(NImNHPtBu)] as the most active catalyst. With its stable Ru-BH4 analogue, in which chloride is replaced by BH4, a broad range of (hetero)aromatic and aliphatic nitriles, including industrially interesting adiponitrile, has been hydrogenated under mild and base-free conditions.
Adam, Rosa,Alberico, Elisabetta,Baumann, Wolfgang,Drexler, Hans-Joachim,Jackstell, Ralf,Junge, Henrik,Beller, Matthias
p. 4991 - 5002
(2016/04/05)

Efficient Reduction of C–N Multiple Bonds Catalyzed by Magnetically Retrievable Magnetite Nanoparticles with Sodium Borohydride
Abstract: A simple, rapid and efficient methodology has been developed for the reductive transformation of the compounds bearing C–N multiple bonds such as oximes and nitriles to the corresponding amines by sodium borohydride catalyzed by highly active solid Fe3O4 nanoparticles. The catalyst was easily recovered using external magnet and reused five times without losing its catalytic activity. Graphical Abstract: A simple, rapid, efficient and reusable heterogeneous catalytic system has been developed for the reductive transformation of oximes and nitriles into corresponding amines by sodium borohydride in presence of Fe3O4 nanoparticles.[Figure not available: see fulltext.]
Kumari, Pratibha,Gautam, Renu,Yadav, Harshit,Kushwaha, Vikas,Mishra, Avinash,Gupta, Shilpi,Arora, Veena
p. 2149 - 2156
(2016/10/18)

Mild and Selective Cobalt-Catalyzed Chemodivergent Transfer Hydrogenation of Nitriles
Herein, we describe a selective cobalt-catalyzed chemodivergent transfer hydrogenation of nitriles to synthesize primary, secondary, and tertiary amines. The solvent effect plays a key role for the selectivity control. The general applicability of this procedure was highlighted by the synthesis of more than 70 amine products bearing various functional groups in high chemoselectivity. Moreover, this mild system achieved >2000 TONs (turnover numbers) for the transfer hydrogenation of nitriles.
Shao, Zhihui,Fu, Shaomin,Wei, Mufeng,Zhou, Shaolin,Liu, Qiang
supporting information
p. 14653 - 14657
(2016/11/23)

Selective hydrogenation of nitriles to primary amines catalyzed by a novel iron complex
Hydrogenation of nitriles to primary amines constitutes an atom-efficient and environmentally benign synthetic reaction. Herein we present a novel complex based on earth-abundant iron, and its application in the catalytic homogeneous hydrogenation of (hetero)aromatic, benzylic, and aliphatic nitriles to selectively form primary amines.
Chakraborty, Subrata,Leitus, Gregory,Milstein, David
supporting information
p. 1812 - 1815
(2016/02/05)