856405-70-4

Upstream product

• 104-94-9 4-methoxy-aniline 
• 1122-91-4 4-bromo-benzaldehyde 
• 873-75-6 4-bromobenzenemethanol 
• 28115-12-0 N-(4-bromobenzylidene)-4-methoxyaniline 
• 2039-82-9 1-bromo-4-ethenyl-benzene 
• 100-17-4 para-methoxynitrobenzene 
• 24856-58-4 1,1-dimethoxy-1-(4-bromophenyl)methane 

Downstream Products

• 1027039-67-3 (2S,3S)-3-(4-Bromo-phenyl)-3-(4-methoxy-phenylamino)-2-methyl-propionaldehyde 
• 929564-38-5 C₂₄H₂₆BrNO₃ 
• 1311140-66-5 2-(4-bromophenyl)-6-methoxy-4-phenylquinoline 
• 28115-12-0 (E)-1-(4-bromophenyl)-N-(4-methoxyphenyl)methanimine 

Relevant academic research and scientific papers

BF3·Et2O as a metal-free catalyst for direct reductive amination of aldehydes with amines using formic acid as a reductant

A versatile metal- and base-free direct reductive amination of aldehydes with amines using formic acid as a reductant under the catalysis of inexpensive BF3·Et2O has been developed. A wide range of primary and secondary amines and diversely substituted aldehydes are compatible with this transformation, allowing facile access to various secondary and tertiary amines in high yields with wide functional group tolerance. Moreover, the method is convenient for the late-stage functionalization of bioactive compounds and preparation of commercialized drug molecules and biologically relevant N-heterocycles. The procedure has the advantages of simple operation and workup and easy scale-up, and does not require dry conditions, an inert atmosphere or a water scavenger. Mechanistic studies reveal the involvement of imine activation by BF3and hydride transfer from formic acid.

Half-Sandwich Ru(II) Complexes with N,O-Chelate Ligands: Diverse Catalytic Activity for Amine Synthesis in Water

Several types of β-ketoamino based N,O-coordinate half-sandwich ruthenium complexes have been synthesized in moderate to good yields. The stable ruthenium complexes displayed good and diverse catalytic efficiency in reductive amination between aldehydes and amines in aqueous solution. The method gave a facile route for one-pot synthesis of diverse complicated amines with a low catalyst loading by using cheap and less-toxic HCOOH or clean H2 as hydrogen source. Catalyst Ru1 showed the highest catalytic activity of 190 h-1 TOF value in the reductive amination reaction of benzaldehyde with aniline. The corresponding amine products were furnished in excellent yields under the standard catalysis system. The efficient and diverse catalytic activity, broad substance scope, mild conditions, and environmentally benign solvent made this system potentially applicable in industrial production. Ruthenium complexes were characterized using NMR, elemental analysis, and IR techniques to confirm their structure.

NEW METHOD FOR THE SYNTHESIS OF UNSYMMETRICAL TERTIARY AMINES

Disclosed is a new method for the synthesis of unsymmetrical tertiary amines using alcohol and an imine, and to new tertiary amines.

Iron-Catalyzed Nitrene Transfer Reaction of 4-Hydroxystilbenes with Aryl Azides: Synthesis of Imines via C=C Bond Cleavage

C=C bond breaking to access the C=N bond remains an underdeveloped area. A new protocol for C=C bond cleavage of alkenes under nonoxidative conditions to produce imines via an iron-catalyzed nitrene transfer reaction of 4-hydroxystilbenes with aryl azides is reported. The success of various sequential one-pot reactions reveals that the good compatibility of this method makes it very attractive for synthetic applications. On the basis of experimental observations, a plausible reaction mechanism is also proposed.

Phosphine-Free Well-Defined Mn(I) Complex-Catalyzed Synthesis of Amine, Imine, and 2,3-Dihydro-1 H-perimidine via Hydrogen Autotransfer or Acceptorless Dehydrogenative Coupling of Amine and Alcohol

The application of nontoxic, earth-abundant transition metals in place of costly noble metals is a paramount goal in catalysis and is especially interesting if the air- and moisture-stable ligand scaffold is used. Herein, we report the synthesis of amines/imines directly from alcohol and amines via hydrogen autotransfer or acceptorless dehydrogenation catalyzed by well-defined phosphine-free Mn complexes. Both imines and amines can be obtained from the same set of alcohols and amines using the same catalyst, only by tuning the reaction conditions. The amount and nature of the base are found to be a highly important aspect for the observed selectivity. Both the primary and secondary amines have been employed as substrates for the N-alkylation reaction. As a highlight, we showed the chemoselective synthesis of resveratrol derivatives. Furthermore, the Mn-catalyzed dehydrogenative synthesis of structurally important 2,3-dihydro-1H-perimidines has also been demonstrated. Density functional theory calculations were also carried out to model the reaction path and to calculate the reaction profile.

Enhanced Catalytic Activity of Oxygen-Tethered IrIII NHC Complexes in Aqueous Transfer Hydrogenative Reductive Amination Reactions: Experimental Kinetic and Mechanistic Study

The synthesis and characterization of seven new IrIII complexes containing o-phenoxide or o-naphthoxide chelated N-heterocyclic carbene ligands is reported herein. The crystal structures of six of the complexes have been determined. These complexes efficiently catalyze the transfer hydrogenative reductive amination (RA) of carbonyls and amines in water. Amongst the complexes tested, the introduction of o-naphthoxide on a nitrogen atom of imidazole based NHC ligand greatly increased the catalytic activity. The catalytic system has a broad substrate scope, which allows the synthesis of a variety of amines in excellent yields and with high turnover numbers up to 490 (for ketones) and 14800 (for aldehydes). The mechanism of aqueous RA reaction with an o-aryloxide chelated NHC-IrIII catalyst has been investigated by NMR spectroscopy and kinetic measurements. These studies suggest that the transfer hydrogenation (TH) is turnover-limited by the hydride formation step. As a result of the 1H NMR studies, the higher catalytic activity of o-naphthoxide chelated catalyst (3 g) over o-phenoxide chelated one (3 b) can be attributed partly due to the faster formation of an iridium hydride, the key intermediate in the RA reactions.

A process for preparing amine compound using carbon-supported cobalt-rhodium nanoparticel catalyzed hydrogen-free recuctive amination

The present invention relates to hydrogen-free reductive amination of an aldehyde and/or ketone and an amine and/or nitroarene using cobalt-rhodium heterometal nanoparticles supported on carbon as a non-homogeneous catalyst. According to the present invention, it is possible to carry out amination under significantly lower pressure as compared to the reductive amination carried out in the presence of a conventional rhodium or ruthenium catalyst. In addition, there is no need for using an additional ligand, acid or base. Further, it is possible to use water generated in a reaction system by a water-gas shift reaction as a hydrogen source with no use of an external hydrogen source, and thus to use a solvent without purification. Thus, it is possible to simplify the reaction procedure. The catalyst system according to the present invention provides a simple method for preparing secondary and tertiary amines from various aldehydes and amines.

Synthesis of N-benzyl-N-phenylthiophene-2-carboxamide analogues as a novel class of enterovirus 71 inhibitors

A series of novel human enterovirus 71 inhibitors, N-benzyl-N-phenylthiophene-2-carboxamide analogues, were synthesized and their antiviral activities were evaluated in vitro. Most derivatives of this structure against EV71 had a low micromolar range in the RD (rhabdomyosarcoma) cell lines. The most potent compound 5a, N-(4-bromobenzyl)-N-(4-fluorophenyl)thiophene-2-carboxamide, showed low micromolar activity against EV71 (EC50 = 1.42 μM) compared to the reference anti-EV71 drug enviroxime (EC50 = 0.15 μM). Preliminary SAR studies revealed that the thiophene-2-carboxamide core is crucial for maintaining antiviral activity, and N-substituent phenyl groups largely influenced the anti-EV71 efficacy of this new class of potent antiviral agents.

A New Phenoxide Chelated IrIII N-Heterocyclic Carbene Complex and Its Application in Reductive Amination Reactions

A new phenoxide chelated [Ir(NHC)CpCl] (NHC = N-heterocyclic carbene; Cp = pentamethylcyclopentadienyl) complex (3) has been prepared by reaction of [IrCpCl2]2 with an in situ prepared NHC-Ag complex in dichloromethane at ambient temperature. The IrIII complex was stable toward air and moisture and was fully characterized by 1H, 13C NMR, HRMS, and single-crystal X-ray diffraction. The new complex was found to be an active catalyst for transfer hydrogenative reductive amination under aqueous conditions with formate as hydrogen source as well as hydrogenative reductive amination reactions using H2. Various carbonyl compounds such as aliphatic and aromatic ketones and aldehydes were successfully reacted with amines to give new amines. In comparison with transfer hydrogenative reductive amination, the reductive amination with H2 is faster and permits higher molar ratios of the substrate to the catalyst (S/C).

NaBH4/PhCO2H: An efficient system for reductive amination of aldehydes

NaBH4/PhCO2H system has been used for thereductive aminationofa varietyof aldehydes withanilines. The reductive amination reactions have been performed within 60-120 min in THFunder reflux conditionsin high to excellent yields of products (85-95%).