86386-67-6

Upstream product

• 1188-33-6 N,N-dimethylformamide diethyl diacetal 
• 201230-82-2 carbon monoxide 
• 104-86-9 4-chlorobenzylamine 
• 67-56-1 methanol 
• 68-12-2 N,N-dimethyl-formamide 
• 104-88-1 4-chlorobenzaldehyde 
• 77287-34-4 formamide 
• 124-38-9 carbon dioxide 
• 64-18-6 formic acid 
• 623-03-0 4-Cyanochlorobenzene 
• 109-94-4 formic acid ethyl ester 

Downstream Products

• 3472-78-4 3-(4-Chlorphenyl)-1,1,3,3-tetrachlor-2-aza-propen-⁽¹⁾ 
• 104936-73-4 N-methyl-N-[(4-chlorophenyl)methyl]formamide 
• 39546-47-9 p-chlorobenzylisocyanide 
• 104936-82-5 2-(4-chloro-phenyl)-1-methyl-pyrrolidine 
• 104936-48-3 [1-(4-Chloro-phenyl)-pentyl]-methyl-amine 
• 3358-37-0 2-(4-chloro-phenyl)-1-methyl-piperidine 
• 104936-75-6 N'-tert-Butyl-N-(4-chloro-benzyl)-N-methyl-formamidine 
• 1175033-55-2 N-[(4-chlorophenyl)methyl]thioformamide 

Relevant academic research and scientific papers

Chromium-catalysed efficient: N -formylation of amines with a recyclable polyoxometalate-supported green catalyst

A simple and efficient protocol for the formylation of amines with formic acid, catalyzed by a polyoxometalate-based chromium catalyst, is described. Notably, this method shows excellent activity and chemoselectivity for the formylation of primary amines; diamines have also been successfully employed. Importantly, the chromium catalyst is potentially non-toxic, environmentally benign and safer than the widely used high valence chromium catalysts such as CrO3 and K2Cr2O7. The catalyst can be recycled several times with a negligible impact on activity. Finally, a plausible mechanism is provided based on the observation of intermediate and control experiments.

An efficient way for the: N -formylation of amines by inorganic-ligand supported iron catalysis

The first example of an inorganic-ligand supported iron(iii) catalysed coupling of formic acid and amines to form formamides is reported. The pure inorganic catalyst (NH4)3[FeMo6O18(OH)6] (1), which consists of a central FeIII single-atomic core supported within a cycle-shaped inorganic ligand consisting of six MoVIO6 octahedra, shows excellent activity and selectivity, and avoids the use of complicated/commercially unavailable organic ligands. Various primary amines and secondary amines have been successfully transformed into the corresponding formamides under mild conditions, and the formylation of primary diamines has also been achieved for the first time. The Fe catalyst 1 can be reused several times without appreciable loss of activity.

A NHC-silyliumylidene cation for catalytic N?formylation of amines using carbon dioxide

This study describes the use of a silicon(II) complex, namely, the NHC-silyliumylidene cation complex [(IMe)2SiH]I (1, IMe =:C{N(Me)C(Me)}2), to catalyze the chemoselective N-formylation of primary and secondary amines using CO2 and PhSiH3 under mild conditions to afford the corresponding formamides as a sole product (average reaction time: 4.5 h; primary amines, average yield: 95%, average TOF: 8 h?1; secondary amines, average yield: 98%, average TOF: 17 h?1). The activity of 1 and product yields outperform the currently available non-transition-metal catalysts used for this catalysis. Mechanistic studies show that the silicon(II) center in complex 1 catalyzes the C?N bond formation via a different pathway in comparison with non-transition-metal catalysts. It sequentially activates CO2, PhSiH3, and amines, which proceeds via a dihydrogen elimination mechanism, to form formamides, siloxanes, and dihydrogen gas.

Tetracoordinate borates as catalysts for reductive formylation of amines with carbon dioxide

We report sodium trihydroxyaryl borates as the first robust tetracoordinate organoboron catalysts for reductive functionalization of CO2. These catalysts, easily synthesized from condensing boronic acids with metal hydroxides, activate main group element-hydrogen (E-H) bonds efficiently. In contrast to BX3 type boranes, boronic acids and metal-BAr4 salts, under transition metal-free conditions, sodium trihydroxyaryl borates exhibit high reactivity of reductive N-formylation toward a variety of amines (106 examples), including those with functional groups such as ester, olefin, hydroxyl, cyano, nitro, halogen, MeS-, ether groups, etc. The over-performance to catalyze formylation of challenging pyridyl amines affords a promising alternative method to the use of traditional formylation reagents. Mechanistic investigation supports electrostatic interactions as the key for Si/B-H activation, enabling alkali metal borates as versatile catalysts for hydroborylation, hydrosilylation, and reductive formylation/methylation of CO2.

One-step synthesis of N, N′-substituted 4-imidazolidinones by an isocyanide-based pseudo-five-multicomponent reaction

A pseudo-five-multicomponent reaction involving an isocyanide, a primary amine, two molecules of formaldehyde and water is reported, which gives N,N′-substituted 4-imidazolidinones when trifluoroethanol is used as the solvent. The reaction proceeds with good yields and with a wide variety of amines and isocyanides, providing an efficient new entry to these heterocycles. A preliminary study of the reaction mechanism suggests that trifluoroethanol, although acting as the solvent, is directly involved as a reagent in the reaction pathway.

Ethanol-mediated N-formylation of amines with CO2/H2 over cobalt catalysts

The CO2-involved synthesis of chemicals is of great significance from a green and sustainable point of view. Herein, we present an efficient Co-based catalytic system composed of a commercially available Co salt, the tetradentate phosphine ligand P-(CH2CH2PPh2)3, and a base, denoted as [Co]/PP3/base, for the synthesis of formamides via the formylation of amines with CO2/H2. It was indicated that the selectivity of products (i.e., formamide or methylamine) could be tuned to some extent via changing the solvent and the base. Using ethanol as the solvent, the Co(ClO4)2·6H2O/PP3/K2CO3 system showed high activity for the production of formamides, affording product yields of 82-95%, together with its broad substrate scope. Exploration of the reaction mechanism indicated that formamide was formed with HCOOH as the intermediate, while the methylamine byproduct was produced with HCHO as the intermediate via the hydrogenolysis of dialkylaminomethane.

Diverse catalytic reactivity of a dearomatized PN3P?-nickel hydride pincer complex towards CO2 reduction

A dearomatized PN3P?-nickel hydride complex has been prepared using an oxidative addition process. The first nickel-catalyzed hydrosilylation of CO2 to methanol has been achieved, with unprecedented turnover numbers. Selective methylation and formylation of amines with CO2 were demonstrated by such a PN3P?-nickel hydride complex, highlighting its versatile functions in CO2 reduction.

Rational design and synthesis of 1,5-disubstituted tetrazoles as potent inhibitors of the MDM2-p53 interaction

Using the computational pharmacophore-based ANCHOR.QUERY platform a new scaffold was discovered. Potent compounds evolved inhibiting the protein-protein interaction p53-MDM2. An extensive SAR study was performed based on our four-point pharmacophore model

A Titanium Dioxide Supported Gold Nanoparticle Catalyst for the Selective N-Formylation of Functionalized Amines with Carbon Dioxide and Hydrogen

A TiO2-supported, gold nanoparticle catalyst was found to allow the N-formylation of various amines, including normally unreactive anilines, by using CO2 as the carbonyl source under a H2 atmosphere. A series of reducible functional groups, such as olefins, halogens, carbonyls, carbamates, and cyano moieties, were completely retained during the formylation, which proved the highly selective nature of the formylation reaction. The catalyst was also found to be reusable without any loss of activity or selectivity.

Manganese-Catalyzed N-Formylation of Amines by Methanol Liberating H2: A Catalytic and Mechanistic Study

The first example of a base metal (manganese) catalyzed acceptorless dehydrogenative coupling of methanol and amines to form formamides is reported herein. The novel pincer complex (iPr-PNHP)Mn(H)(CO)2 catalyzes the reaction under mild conditions in the absence of any additives, bases, or hydrogen acceptors. Mechanistic insight based on the observation of an intermediate and DFT calculations is also provided.