Stable Preformed Chiral Palladium Catalysts for the One-Pot Asymmetric Reductive Amination of Ketones

Dibenzylamine motifs are an important class of crucial organic compounds and are widely used in fine chemical and pharmaceutical industries. The development of the efficient, economical, and environmentally friendly synthesis of amines using transition metal-based heterogeneous catalysts remains both desirable and challenging. Herein, we prepared the covalent organic framework (COF)-supported heterogeneous reduced COF-supported Pd-based catalyst and used it for the one-pot reductive amination of aldehydes. There are both Pd metallic state and oxidated Pdσ+ in the catalysts. Furthermore, in the presence of the reduced COF-supported Pd-based catalyst, many aromatic, aliphatic, and heterocyclic aldehydes with various functional groups substituted were converted to their corresponding amines products in good to excellent selectivity (up to 91%) under mild reaction conditions (70 °C, 2 h, NH3, 20 bar H2). This work expands the covalent organic frameworks for the material family and its support catalyst, opening up new catalytic applications in the economical, practical, and effective synthesis of secondary amines.

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Intermetallic Ni2Si/SiCN as a highly efficient catalyst for the one-pot tandem synthesis of imines and secondary amines

Inorganic Chemistry Frontiers ◽

10.1039/c9qi01077g ◽

2020 ◽

Vol 7 (1) ◽

pp. 82-90 ◽

Cited By ~ 1

Author(s):

Xiao Chen ◽

Shuhua Han ◽

Dongdong Yin ◽

Changhai Liang

Keyword(s):

High Activity ◽

Aromatic Amine ◽

Reductive Amination ◽

High Selectivity ◽

Secondary Amines ◽

One Pot ◽

Efficient Catalyst ◽

Highly Efficient ◽

The One ◽

Tandem Synthesis

For the one-pot reductive amination of benzaldehyde with nitrobenzene, intermetallic Ni2Si/SiCN from the decomposition of a nickel-modified polysilazane precursor exhibited high activity (>99%) and high selectivity (92% to aromatic amine).

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One-pot, chemoselective synthesis of secondary amines from aryl nitriles using a PdPt–Fe3O4 nanoparticle catalyst

Catalysis Science & Technology ◽

10.1039/d0cy00630k ◽

2020 ◽

Vol 10 (13) ◽

pp. 4201-4209

Author(s):

Jin Hee Cho ◽

Sangmoon Byun ◽

Ahra Cho ◽

B. Moon Kim

Keyword(s):

Reductive Amination ◽

Secondary Amines ◽

Fe3o4 Nanoparticle ◽

Catalytic Method ◽

One Pot ◽

Chemoselective Synthesis ◽

Aryl Nitriles ◽

The One ◽

Nanoparticle Catalyst

We have developed a new catalytic method for the one-pot, cascade synthesis of unsymmetrical secondary amines via the reductive amination of aryl nitriles with nitroalkanes using a PdPt–Fe3O4 nanoparticle (NP) catalyst.

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Chemicals from Biomass: Selective Synthesis of N-Substituted Furfuryl Amines by the One-Pot Direct Reductive Amination of Furanic Aldehydes

ACS Sustainable Chemistry & Engineering ◽

10.1021/acssuschemeng.8b06631 ◽

2019 ◽

Vol 7 (6) ◽

pp. 6243-6250 ◽

Cited By ~ 15

Author(s):

Andrea García-Ortiz ◽

Juan D. Vidal ◽

Maria J. Climent ◽

Patricia Concepción ◽

Avelino Corma ◽

...

Keyword(s):

Reductive Amination ◽

Selective Synthesis ◽

One Pot ◽

The One

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Palladium-catalyzed 2,5-diheteroarylation of 2,5-dibromothiophene derivatives

Beilstein Journal of Organic Chemistry ◽

10.3762/bjoc.10.309 ◽

2014 ◽

Vol 10 ◽

pp. 2912-2919 ◽

Cited By ~ 9

Author(s):

Fatma Belkessam ◽

Aidene Mohand ◽

Jean-François Soulé ◽

Abdelhamid Elias ◽

Henri Doucet

Keyword(s):

Palladium Catalysts ◽

One Pot ◽

Palladium Catalyzed ◽

The One

Conditions allowing the one pot 2,5-diheteroarylation of 2,5-dibromothiophene derivatives in the presence of palladium catalysts are reported. Using KOAc as the base, DMA as the solvent and only 0.5–2 mol % palladium catalysts, the target 2,5-diheteroarylated thiophenes were obtained in moderate to good yields and with a wide variety of heteroarenes such as thiazoles, thiophenes, furans, pyrroles, pyrazoles or isoxazoles. Moreover, sequential heteroarylation reactions allow the access to 2,5-diheteroarylated thiophenes bearing two different heteroaryl units.

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3-(tert-Butyl)-N-(4-methoxybenzyl)-1-methyl-1H-pyrazol-5-amine

Molbank ◽

10.3390/m1196 ◽

2021 ◽

Vol 2021 (1) ◽

pp. M1196

Author(s):

Diana Becerra ◽

Hugo Rojas ◽

Juan-Carlos Castillo

Keyword(s):

Reductive Amination ◽

2D Nmr ◽

Reduction Reaction ◽

Reaction Sequence ◽

One Pot ◽

Isolation And Purification ◽

Tert Butyl ◽

The One ◽

Synthetic Intermediate

We reported an efficient one-pot two-step synthesis of 3-(tert-butyl)-N-(4-methoxybenzyl)-1-methyl-1H-pyrazol-5-amine 3 in good yield by a solvent-free condensation/reduction reaction sequence starting from 3-(tert-butyl)-1-methyl-1H-pyrazol-5-amine 1 and p-methoxybenzaldehyde 2. The one-pot reductive amination proceeded by the formation in situ of the N-(5-pyrazolyl)imine 4 as key synthetic intermediate of other valuable pyrazole derivatives. This methodology is distinguished by its operational easiness, short reaction time, isolation and purification of the aldimine intermediate is not required. The structure of the synthesized N-heterocyclic amine 3 was fully characterized by FTIR-ATR, 1D and 2D NMR experiments, EIMS, and elemental analysis.

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Metal-based Heterogeneous Catalysts for One-Pot Synthesis of Secondary Anilines from Nitroarenes and Aldehydes

Molecules ◽

10.3390/molecules26041120 ◽

2021 ◽

Vol 26 (4) ◽

pp. 1120

Author(s):

Giuseppe Romanazzi ◽

Valentina Petrelli ◽

Ambra Maria Fiore ◽

Piero Mastrorilli ◽

Maria Michela Dell’Anna

Keyword(s):

Heterogeneous Catalysts ◽

Reductive Amination ◽

State Of The Art ◽

Pharmaceutical Products ◽

Subsequent Reduction ◽

Substituted Anilines ◽

One Pot ◽

Aryl Amines ◽

The One ◽

Simple Reduction

Recently, N-substituted anilines have been the object of increasing research interest in the field of organic chemistry due to their role as key intermediates for the synthesis of important compounds such as polymers, dyes, drugs, agrochemicals and pharmaceutical products. Among the various methods reported in literature for the formation of C–N bonds to access secondary anilines, the one-pot reductive amination of aldehydes with nitroarenes is the most interesting procedure, because it allows to obtain diverse N-substituted aryl amines by simple reduction of nitro compounds followed by condensation with aldehydes and subsequent reduction of the imine intermediates. These kinds of tandem reactions are generally catalyzed by transition metal-based catalysts, mainly potentially reusable metal nanoparticles. The rapid growth in the last years in the field of metal-based heterogeneous catalysts for the one-pot reductive amination of aldehydes with nitroarenes demands for a review on the state of the art with a special emphasis on the different kinds of metals used as catalysts and their recyclability features.

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A Series of Metal-Organic Frameworks for Selective CO2 Capture and Catalytic Oxidative Carboxylation of Olefins

10.26434/chemrxiv.7068509 ◽

2018 ◽

Author(s):

Huong T. D. Nguyen ◽

Y B. N. Tran ◽

Hung N. Nguyen ◽

Tranh C. Nguyen ◽

Felipe Gándara ◽

...

Keyword(s):

Room Temperature ◽

Gas Adsorption ◽

New Materials ◽

One Pot ◽

Acid Gas ◽

Naphthalene Diimide ◽

Styrene Carbonate ◽

Metal Organic ◽

Adsorption Of Co ◽

The One

Three novel lanthanide metal˗organic frameworks (Ln-MOFs), namely MOF-590, -591, and -592 were constructed from a naphthalene diimide tetracarboxylic acid. Gas adsorption measurements of MOF-591 and -592 revealed good adsorption of CO2 (low pressure, at room temperature) and moderate CO2 selectivity over N2 and CH4. Accordingly, breakthrough measurements were performed on a representative MOF-592, in which the separation of CO2 from binary mixture containing N2 and CO2 was demonstrated without any loss in performance over three consecutive cycles. Moreover, MOF-590, MOF-591, and MOF-592 exhibited catalytic activity in the one-pot synthesis of styrene carbonate from styrene and CO2 under mild conditions (1 atm CO2, 80 °C, and solvent-free). Among the new materials, MOF-590 revealed a remarkable efficiency with exceptional conversion (96%), selectivity (95%), and yield (91%).

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A Study on the Rearrangement of Dialkyl 1-Aryl-1-hydroxymethylphosphonates to Benzyl Phosphates

Current Organic Chemistry ◽

10.2174/1385272824666200226114306 ◽

2020 ◽

Vol 24 (4) ◽

pp. 465-471 ◽

Cited By ~ 2

Author(s):

Zita Rádai ◽

Réka Szabó ◽

Áron Szigetvári ◽

Nóra Zsuzsa Kiss ◽

Zoltán Mucsi ◽

...

Keyword(s):

Quantum Chemical ◽

Room Temperature ◽

Phase Transfer ◽

One Pot ◽

Substrate Dependence ◽

Triethylbenzylammonium Chloride ◽

One Step ◽

The Pudovik Reaction ◽

The One ◽

Solid Liquid

The phospha-Brook rearrangement of dialkyl 1-aryl-1-hydroxymethylphosphonates (HPs) to the corresponding benzyl phosphates (BPs) has been elaborated under solid-liquid phase transfer catalytic conditions. The best procedure involved the use of triethylbenzylammonium chloride as the catalyst and Cs2CO3 as the base in acetonitrile as the solvent at room temperature. The substrate dependence of the rearrangement has been studied, and the mechanism of the transformation under discussion was explored by quantum chemical calculations. The key intermediate is an oxaphosphirane. The one-pot version starting with the Pudovik reaction has also been developed. The conditions of this tandem transformation were the same, as those for the one-step HP→BP conversion.

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