1699-52-1

Upstream product

• 119-65-3 isoquinoline 
• 64-18-6 formic acid 
• 121-44-8 triethylamine 
• 201230-82-2 carbon monoxide 
• 91-21-4 1,2,3,4-tetrahydroisoquinoline 
• 75-87-6 chloral 
• 109-94-4 formic acid ethyl ester 
• 50-00-0 formaldehyd 
• 23069-99-0 N-(2-phenylethyl)formamide 
• 191545-92-3 1,2,3,4-tetrahydro-2-formyl-4-phenylthioisoquinoline 
• 77287-34-4 formamide 
• 3230-65-7 3,4-dihydroisoquinoline 
• 598-30-1 sec.-butyllithium 
• 199480-42-7 1,2,3,4-tetrahydroisoquinolin-2-ylcarbonyl chloride 

Downstream Products

• 84010-64-0 N'd-(+)-(α-methylbenzylamino)-1,2,3,4-tetrahydroisoquinoline formamidine 
• 130901-44-9 [1-(3,4-Dihydro-1H-isoquinolin-2-yl)-meth-(E)-ylidene]-((S)-1-methoxymethyl-2-phenyl-ethyl)-amine 
• 91-21-4 1,2,3,4-tetrahydroisoquinoline 
• 1612-65-3 2-methyl-1,2,3,4-tetrahydroisoquinoline 
• 84010-77-5 [1-[(S)-1-(4-Chloro-butyl)-3,4-dihydro-1H-isoquinolin-2-yl]-meth-(E)-ylidene]-((R)-2-phenyl-2-trimethylsilanyloxy-1-trimethylsilanyloxymethyl-ethyl)-amine 
• 3340-78-1 2-phenyl-1,2,3,4-tetrahydroisoquinoline 
• 84010-77-5 [1-[(R)-1-(4-Chloro-butyl)-3,4-dihydro-1H-isoquinolin-2-yl]-meth-(E)-ylidene]-((1S,2S)-2-phenyl-2-trimethylsilanyloxy-1-trimethylsilanyloxymethyl-ethyl)-amine 
• 84010-77-5 [1-[(S)-1-(4-Chloro-butyl)-3,4-dihydro-1H-isoquinolin-2-yl]-meth-(E)-ylidene]-((1S,2S)-2-phenyl-2-trimethylsilanyloxy-1-trimethylsilanyloxymethyl-ethyl)-amine 

Relevant academic research and scientific papers

Pd/C-catalyzed reductive formylation of indoles and quinolines using formic acid

A two-step, one-pot domino reaction methodology was developed to synthesize a variety of N-formylindolines and N-formyltetrahydroquinolines from the corresponding indoles and quinolines. In the first step, the heterocyclic compounds are reduced to the corresponding dihydro or tetrahydro products by a Pd/C-catalyzed transfer hydrogenation using formic acid as a hydrogen donor. In the second step, nitrogen is formylated by formic acid to afford the final products in very good isolated yields. Georg Thieme Verlag Stuttgart New York.

N-formylation of amines using phenylsilane and CO2 over ZnO catalyst under mild condition

Several research studies have been conducted on N-formylation of amines using phenylsilane and CO2. However, most of these studies involved tedious processes of catalyst preparation or complex procedures. In the present study, we describe the use of a simple and commercially available ZnO catalyst for selective N-formylation of amines under mild condition. High-yielding N-formylation products with good recyclability and wide substrate scope were obtained, which can promote fine chemical synthesis and CO2 capture.

Hydrogenation of Anthracene and Nitrogen Heterocycles Catalyzed by Iron Pentacarbonyl under Water-Gas Conditions

Iron pentacarbonyl in the presence of H2O, CO, base and a phase-transfer agent catalyzes the reduction of quinoline regiospecifically in the nitrogen-containing ring at temperaturee between 150 and 300 deg C.The best yield ( 87 turnovers) is obtained in the presence of 18-crown-6 ether as phase-transfer agent.Anthracene is reduced to 9,10-dihydroanthracene by the same system, which becomes catalytic (17 turnovers) with the addition of bipyridine or terpyridine and tetra-n-butylammonium iodide as phase-transfer agent.The phenanthrolines (4,7 or 1,10) are also regiospecifically reduced in one of the nitrogen-containing rings (71 percent or 50 percent yield, respectively, without optimization).With 9,10-dimethylanthracene, nearly equal amounts of both cis- and trans-9,10-dihydro-9,10-dimethylanthracene are obtained.Aromatic coal constituents such as pyrene, chrysene, or dibenzothiophene are not reduced under these conditions; a reduction potential > -2.0 V seems to be required to achieve hydrogenation in this system.A electron-transfer process is indicated.

Copper-Catalyzed Formylation of Amines by using Methanol as the C1 Source

Cu/TEMPO catalyst systems are known for the selective transformation of alcohols to aldehydes, as well as for the simultaneous coupling of alcohols and amines to imines under oxidative conditions. In this study, such a Cu/TEMPO catalyst system is found to catalyze the N-formylation of a variety of amines by initial oxidative activation of methanol as the carbonyl source via formaldehyde and formation of N,O-hemiacetals and oxidation of the latter under very mild conditions. A vast range of amines, including aromatic and aliphatic, primary and secondary, and linear and cyclic amines are formylated under these conditions with good to excellent yields. Moreover, paraformaldehyde can be used instead of methanol for the N-formylation.

Heterogeneous Cobalt-Catalyzed Direct N-Formylation of Isoquinolines with CO2 and H2

Isoquinolines (IQs) are an abundant feedstock, and N-formyl-1,2,3,4-tetrahydroisoquinolines (FTHIQs) are valuable fine chemicals and key intermediates. Herein, we report for the first time the Co0/ZnCl2-catalyzed direct N-formylation of IQs by using CO2 with H2 to produce FTHIQs. It was discovered that the Co catalyst and ZnCl2 worked synergistically in catalyzing the N-formylation reactions, and moderate to high yields of the desired products could be obtained, depending on the nature of the substrates. The Co0 catalyst could be reused at least five times without a notable decrease in activity. A possible reaction mechanism is proposed on the basis of control experiments.

Selective Iron-Catalyzed N-Formylation of Amines using Dihydrogen and Carbon Dioxide

A family of iron(II) carbonyl hydride species supported by PNP pincer ligands was identified as highly productive catalysts for the N-formylation of amines via CO2 hydrogenation. Specifically, iron complexes supported by two different types of PNP ligands were examined for formamide production. Complexes containing a PNP ligand with a tertiary amine afforded superior turnover numbers in comparison to complexes containing a bifunctional PNP ligand with a secondary amine, indicating that bifunctional motifs are not required for catalysis. Systems incorporating a tertiary amine containing a PNP ligand were active for the N-formylation of a variety of amine substrates, achieving TONs up to 8900 and conversions as high as 92%. Mechanistic experiments suggest that N-formylation occurs via an initial, reversible reduction of CO2 to ammonium formate followed by dehydration to produce formamide. Several intermediates relevant to this reaction pathway, as well as iron-containing deactivation species, were isolated and characterized.

Nickel-Catalyzed Amination of Aryl Chlorides with Amides

A nickel-catalyzed amination of aryl chlorides with diverse amides via C-N bond cleavage has been realized under mild conditions. A broad substrate scope with excellent functional group tolerance at a low catalyst loading makes the protocol powerful for synthesizing various aromatic amines. The aryl chlorides could selectively couple to the amino fragments rather than the carbonyl moieties of amides. Our protocol complements the conventional amination of aryl chlorides and expands the usage of inactive amides.

Highly Efficient and Selective N-Formylation of Amines with CO2 and H2 Catalyzed by Porous Organometallic Polymers

The valorization of carbon dioxide (CO2) to fine chemicals is one of the most promising approaches for CO2 capture and utilization. Herein we demonstrated a series of porous organometallic polymers could be employed as highly efficient and recyclable catalysts for this purpose. Synergetic effects of specific surface area, iridium content, and CO2 adsorption capability are crucial to achieve excellent selectivity and yields towards N-formylation of diverse amines with CO2 and H2 under mild reaction conditions even at 20 ppm catalyst loading. Density functional theory calculations revealed not only a redox-neutral catalytic pathway but also a new plausible mechanism with the incorporation of the key intermediate formic acid via a proton-relay process. Remarkably, a record turnover number (TON=1.58×106) was achieved in the synthesis of N,N-dimethylformamide (DMF), and the solid catalysts can be reused up to 12 runs, highlighting their practical potential in industry.

Catalytically Active Co?Nx Species Stabilized on Nitrogen-doped Porous Carbon for Efficient Hydrogenation and Dehydrogenation of N-heteroarenes

The development of bifunctional, highly active and stable non-noble-metal catalysts is important for synthetic chemistry. In this study, a highly dispersed Co catalyst stabilized on the mesoporous N-doped carbon layers was prepared by adsorption and pyrolysis of cobalt complex on dendritic fibrous silica nanospheres (KCC-1@Co?N?C?T). The characterizations of HAADF-STEM, XRD and XPS together with the KSCN poisoning tests determine the absence of Co0 or CoOx nanoparticles and suggest that the Co?Nx species are the active sites. The formation of Co?Nx species results from the properties of N-rich cobalt-phenanthroline complex and dendritic fibrous silica supports, increasing the original spatial distance between Co atoms and thus preventing them from aggregation. The KCC-1@Co?N?C-800 catalyst showed excellent activity and selectivity for the oxidative dehydrogenation (ODH) of saturated N-heterocycles and base-free catalytic transfer hydrogenation (CTH) of unsaturated N-heterocycles.

Cobalt Nanoparticles Apically Encapsulated by Nitrogen-doped Carbon Nanotubes for Oxidative Dehydrogenation and Transfer Hydrogenation of N-Heterocycles

It is important to develop a highly active and stable transition-metal catalyst with dual-functional properties in the reversible transformations between various saturated and unsaturated N-heterocycles. Herein, we prepared the cobalt nanoparticles (Co NPs) apically encapsulated by the N-doped carbon nanotubes catalyst (Co@NCNTs) via a multiple pyrolysis of low-cost dicyandiamide and cobalt (II) acetylacetonate. The catalyst shows excellent activity and recyclability towards the oxidative dehydrogenation (ODH) and the catalytic transfer hydrogenation (CTH) for various N-heterocycles. The structure of outer N-doped carbon nanotubes (NCNTs) can protect Co NPs from aggregation and leaching. Moreover, the encapsulated Co NPs and the NCNTs may generate a synergistic effect. Both of them facilitate the high performance. The poisoning tests with KSCN were to clarify the different active sites for ODH and CTH reactions: the Co NPs could modify the NCNTs through electrons redistribution, therefore the NCNTs could directly activate O2 in ODH. The encapsulated Co NPs is enhanced by the doped N atoms which is good for the H2 activation in CTH. What's more, the mechanisms of ODH and CTH reactions were also proposed. This work provides a facile and low-cost method to design catalysts, which are dual-functional, highly active and stable, for industrial applications.