4112-09-8

Upstream product

• 22700-22-7 Diethyl-N-(4-methoxycarbonyl-phenyl)-phosphoramidat 
• 100-52-7 benzaldehyde 
• 67-56-1 methanol 
• 149-73-5 trimethyl orthoformate 
• 619-50-1 4-nitrobenzoic acid methyl ester 
• 619-45-4 4-methoxycarbonyl aniline 
• 100-51-6 benzyl alcohol 

Downstream Products

• 5093-85-6 9b-methyl-4t-phenyl-(3aξ,9br)-2,3,3a,4,5,9b-hexahydro-furo[3,2-c]quinoline-8-carboxylic acid methyl ester 
• 5093-85-6 9b-methyl-4c-phenyl-(3aξ,9br)-2,3,3a,4,5,9b-hexahydro-furo[3,2-c]quinoline-8-carboxylic acid methyl ester 
• 97255-67-9 4-{[(1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)-phenyl-methyl]-amino}-benzoic acid methyl ester 
• 123876-56-2 methyl 4-(benzylamino)benzoate 
• 777856-75-4 (1,2-bis(diphenylphosphino)ethane)Rh(PEt₃)[N(C₆H₄COOCH₃)CH(Ph)(p-tolyl)] 
• 619-45-4 4-methoxycarbonyl aniline 

Relevant academic research and scientific papers

Cobalt-Catalyzed Deoxygenative Hydroboration of Nitro Compounds and Applications to One-Pot Synthesis of Aldimines and Amides

The commercially available and bench-stable Co(acac)2 ligated with bis[(2-diphenylphosphino)phenyl] ether (dpephos) was employed for selective room temperature hydroboration of nitro compounds with HBPin (TOF up to 4615 h?1), tolerating halide, hydroxy, amino, ether, ester, lactone, amide and heteroaromatic functionalities. These reactions offered a direct access to a variety of N-borylamines RN(H)BPin, which were in situ treated with aldehydes and carboxylic acids to produce a series of aldimines and secondary carboxamides without the need for dehydrating and/or coupling reagents. Combination of these transformations in a sequential one-pot manner allowed for direct and selective synthesis of aldimines and secondary carboxamides from readily available and inexpensive nitro compounds.

Rhodium catalyzed multicomponent dehydrogenative annulation: one-step construction of isoindole derivatives

A strategy for one-pot synthesis of isoindoles is describedviaa catalytic multicomponent dehydrogenative annulation of diarylimines, vinyl ketones and simple amines. In the presence of a rhodium catalyst and Cu oxidant, four C-H and two N-H bonds are activated along with the formation of one new C-C and two new C-N bonds, leading to a series of isoindole derivatives in good to very high isolated yields.

Method of synthesizing imine and amine compounds by means of borrowing-hydrogen reduction coupling

The invention belongs to energy and chemical industry and particularly relates to a method of synthesizing imine and amine compounds by means of borrowing-hydrogen reduction coupling by using a nitrogen-doped hierarchical-porous biomass-based carbon material supported catalyst. The method includes the steps of: under a seal reaction condition, adding a nitro-aromatic hydrocarbon compound, benzyl alcohol compounds with different substituent groups, the supported catalyst, methylbenzene and potassium tert-butoxide; performing a reaction at 50-150 DEG C for 4-24 h, cooling the product to room temperature and filtering a reaction liquid to obtain the imine compound represented in the formula (1) or the amine compound represented in the formula (2). The raw materials of the catalyst are regenerable resources, are widely distributed, are green and environment-friendly, are easy to prepare and abundant in sources, and are low in cost; the catalyst can be recycled without deactivation and is stable to air, water and heat. By means of the supported metal catalyst, the conversion rate of the borrowing-hydrogen reduction coupling reaction on the nitro-compound and alcohol to prepare the iminecompounds is higher than 99%, and yield can reach 90-60%; the conversion rate of same to prepare the amine compounds is higher than 99%, and yield can reach 90-60%.

Conversion of aldimines to secondary amines using iron-catalysed hydrosilylation

Iron-catalyzed hydrosilylation of imines to amines using a well-defined iron complex is reported. This method employs relatively mild conditions, by reaction of imine, (EtO)3SiH in a 1 : 2 ratio in the presence of 1 mol% precatalyst ([BIAN]Fe(η6-toluene), 3, BIAN = bis(2,6-diisopropylaniline)acenaphthene) at 70 °C. A broad scope of imines was readily converted into the corresponding secondary amines without the need for precatalyst activators.

Umpolung Addition of Aldehydes to Aryl Imines

One of the classical ways to synthesize amines involves the coupling of carbonyl compounds and imines, either through enolate chemistry or acyl-based carbanion equivalents. We herein report an alternative strategy that is based on the use of aldehydes as alkyl carbanion equivalents in a reductive coupling with aryl imines. A wide array of secondary amines can be synthesized in moderate to high yields. This reaction is mediated by hydrazine and catalyzed by ruthenium(II) complexes, and it tolerates various functional groups, such as esters, amides, and nitriles.

A mild and efficient synthesis of substituted quinolines via a cross-dehydrogenative coupling of (Bio)available alcohols and aminoarenes

A ruthenium-catalysed dehydrogenative cross-coupling of primary alcohols and imines in the presence of TFA provided a library of differently substituted quinolines. Imines can be prepared in situ from various anilines and several benzyl alcohols using a ruthenium-catalysed hydrogen-transfer procedure. Without changing the catalyst, quinolines can be obtained in moderate to good yields by adding various primary alcohols in the presence of TFA (30 mol%) via a "telescopic" protocol. The use of alcohols, the absence of strong oxidants and the diversity of potential starting materials make this modern version of the Skraup reaction superior to most of the conventional quinoline syntheses.

Silver-catalyzed alkyne activation: The surprising ligand effect

An unexpected ligand effect was discovered in the silver(I)-catalyzed alkyne activation. For both aldehyde-alkyne-amine (A3) condensation and intermolecular alkyne hydroamination, the type B complex (P:Ag=1:1) effectively promoted the reaction, while no reaction occurred with either no ligand or excess ligands under the identical conditions.

Heteroatom-free arene-cobalt and arene-iron catalysts for hydrogenations

75 years after the discovery of hydroformylation, cobalt catalysts are now undergoing a renaissance in hydrogenation reactions. We have evaluated arene metalates in which the low-valent metal species is - conceptually different from heteroatom-based ligands - stabilized by π coordination to hydrocarbons. Potassium bis(anthracene)cobaltate 1 and -ferrate 2 can be viewed as synthetic precursors of quasi-"naked" anionic metal species; their aggregation is effectively impeded by (labile) coordination to the various π acceptors present in the hydrogenation reactions of unsaturated molecules (alkenes, arenes, carbonyl compounds). Kinetic studies, NMR spectroscopy, and poisoning studies of alkene hydrogenations support the formation of a homogeneous catalyst derived from 1 which is stabilized by the coordination of alkenes. This catalyst concept complements the use of complexes with heteroatom donor ligands for reductive processes. Especially high selectivities were observed in the hydrogenation of various alkenes, ketones, and imines with bis(anthracene) cobaltate(-I) [K(dme)2{Co(C14H10)2}] under mild conditions (1-5 mol% cat., 1-10 bar H2, 20-60°C). Mechanistic studies indicate the operation in alkene hydrogenations of a homogeneous catalyst formed by initial ligand exchange and stabilized by the coordination of π-acidic alkenes or arenes.

Carbonic anhydrase inhibitors. Inhibition of human cytosolic isoforms i and II with (reduced) Schiff's bases incorporating sulfonamide, carboxylate and carboxymethyl moieties

A library of Schiff bases was synthesized by condensation of aromatic amines incorporating sulfonamide, carboxylic acid or carboxymethyl functionalities as Zn2+-binding groups, with aromatic aldehydes incorporating tert-butyl, hydroxy and/or methoxy groups. The corresponding amines were thereafter obtained by reduction of the imines. These compounds were assayed for the inhibition of two cytosolic human carbonic anhydrase (hCA, EC 4.2.1.1) isoenzymes, hCA I and II. The Ki values of the Schiff bases were in the range of 7.0-21,400 nM against hCA II and of 52-8600 nM against hCA I, respectively. The corresponding amines showed Ki values in the range of 8.6 nM-5.3 μM against hCA II, and of 18.7-251 nM against hCA I, respectively. Unlike the imines, the reduced Schiff bases are stable to hydrolysis and several low-nanomolar inhibitors were detected, most of them incorporating sulfonamide groups. Some carboxylates also showed interesting CA inhibitory properties. Such hydrosoluble derivatives may show pharmacologic applications.

Iron-catalyzed synthesis of secondary amines: On the way to green reductive aminations

Amines represent important intermediates in chemical and biological processes. Herein, we describe the use of a nanostructured iron-based catalyst for the tandem reductive amination between nitroarenes and aldehydes using hydrogen as reductant. The nanostructured iron-catalyst is prepared by immobilization of an iron-phenanthroline complex onto a commercially available carbon support. In the reaction sequence a primary amine is formed in situ from the corresponding nitro compound. Reversible condensation with aldehydes forms the respective imines, which are finally reduced to the desired secondary amine. This synthesis of secondary amines is atom-economical and environmentally attractive using cheap and readily available organic compounds as starting materials.