1028783-99-4

Upstream product

• 55-21-0 benzamide 
• 402-49-3 4-bromomethyltrifluoromethylbenzene 
• 3300-51-4 p-Trifluoromethylbenzylamine 
• 65-85-0 benzoic acid 
• 70-11-1 α-bromoacetophenone 
• 16883-69-5 N-phenacylpyridinium bromide 
• 7338-94-5 1,3-diphenyl-2-propynone 
• 136918-14-4 phthalimide 
• 349-95-1 4-(trifluoromethyl)benzylic alcohol 
• 100-47-0 benzonitrile 
• 455-19-6 4-Trifluoromethylbenzaldehyde 
• 455-18-5 4-CF₃C₆H₄CN 
• 98-88-4 benzoyl chloride 
• 94-36-0 dibenzoyl peroxide 

Downstream Products

• 87861-98-1 5-(4-(trifluoromethyl)benzyl)phenanthridin-6(5H)-one 

Relevant academic research and scientific papers

Reductive Amidation without an External Hydrogen Source Using Rhodium on Carbon Matrix as a Catalyst

An efficient method for preparation of secondary amides from primary amides and aldehydes using rhodium on carbon matrix as catalyst was developed. The method does not require any external hydrogen source and carbon monoxide is used as a reducing agent. The most active rhodium catalysts were characterized by BET, TEM and XPS techniques. Unexpectedly, it was found that heterogeneous rhodium on carbon matrix works as precatalyst for homogenous active species due to leaching of rhodium to the solution. Various secondary amides were synthesized and checked for antifungal activity. 4-Methoxy-N-(4-methoxybenzyl)benzamide demonstrated promising activity against Rhizoctonia Solani.

Reductive N-alkylation of primary amides using nickel-nanoparticles

Here we report Ni-nanoparticles as reusable catalysts for reductive N-alkylation of amides. These Ni-nanoparticles based catalysts have been prepared by the template synthesis of tartaric acid and 2-methyl imidazole ligated Ni-complex on SiO2 and subsequent pyrolysis under argon. Applying optimal Ni-nanostructured catalyst, N-alkylation of aromatic and heterocyclic primary amides with different aldehydes in presence of molecular hydrogen was performed to access structurally diverse N-alkylated amides in good to excellent yields. In addition, the applicability of this N-alkylation protocol has been demonstrated for the selective functionalization of primary amide group in Levetiracetam drug.

Atom Transfer Radical Polymerization-Inspired Room Temperature (sp3)C-N Coupling

A simple nonphotochemical procedure is reported for Cu(I)-catalyzed C-N coupling of aliphatic halides with amines and amides. The process is loosely based on the Goldberg reaction but takes place readily at room temperature. It uses Cu(I)Br, a commonly used and inexpensive atom transfer radical polymerization precatalyst, along with the cheap ligand N,N,N′,N″,N″-pentamethyldiethylenetriamine, to activate the R-X bond of the substrate via inner-sphere electron transfer. The procedure brings about productive C-N bond formation between a range of alkyl halide substrates with heterocyclic aromatic amines and amides. The mechanism of the coupling step, which was elucidated through application of computational methods, proceeds via a unique Cu(I) → Cu(II) → Cu(III) → Cu(I) catalytic cycle, involving (a) inner-sphere electron transfer from Cu(I) to the alkyl halide to generate the alkyl radical; (b) successive coordination of the N-nucleophile and the radical to Cu(II); and finally reductive elimination. In the absence of a nucleophile, debrominative homocoupling of the alkyl halide occurs. Control experiments rule out SN-type mechanisms for C-N bond formation.

Silver-Catalyzed Hydroboration of C-X (X = C, O, N) Multiple Bonds

AgSbF6 was developed as an effective catalyst for the hydroboration of various unsaturated functionalities (nitriles, alkenes, and aldehydes). This atom-economic chemoselective protocol works effectively under low catalyst loading, base- A nd solvent-free moderate conditions. Importantly, this process shows excellent functional group tolerance and compatibility with structurally and electronically diverse substrates (>50 examples). Mechanistic investigations revealed that the reaction proceeds via a radical pathway. Further, the obtained N,N-diborylamines were showcased to be useful precursors for amide synthesis.

The synthesis and structure of pyridine-oxadiazole iridium complexes and catalytic applications: Non-coordinating-anion-tuned selective C–N bond formation

Several novel pyridine-oxadiazole iridium complexes were synthesized and characterized through X-ray crystallography. The designed iridium complexes revealed surprisingly high catalytic activity in C–N bondformation of amides and benzyl alcohols with the assistance of non-coordinating anions. In an attempt to achieve borrowing hydrogen reactions of amides with benzyl alcohols, N,N'-(phenylmethylene)dibenzamide products were unexpectedly isolated under non-coordinating anion conditions, whereas N-benzylbenzamide products were achieved in the absence of non-coordinating anions. The mechanism explorations excluded the possibility of “silver effect” (silver-assisted or bimetallic catalysis) and revealed that the reactivity of iridium catalyst was varied by non-coordinating anions. This work provided a convenient and useful methodology that allowed the iridium complex to be a chemoselective catalyst and demonstrated the first example of non-coordinating-anion-tuned selective C–N bond formation

An unprecedented cobalt-catalyzed selective aroylation of primary amines with aroyl peroxides

A novel and facile cobalt-catalyzed selective aroylation of primary amines with aroyl peroxides was developed for the synthesis of aryl amides. It was unprecedented that C[sbnd]N bond formation product was selectively generated without the common N[sbnd]O bond formation product. Aroyl peroxides act as the sole aroylation reagent without additional base or oxidant. The reactions proceeded under mild conditions and showed broad substrates scope with a series of primary amines and aroyl peroxides.

Direct amidation of non-activated carboxylic acid and amine derivatives catalyzed by TiCp2Cl2

This paper described a mild and efficient direct amidation of non-activated carboxylic acid and amine derivatives catalyzed by TiCp2Cl2. Arylacetic acid derivatives reacted with different amines to afford the corresponding amides in good to excellent yield except of aniline. Aryl formic acids failed to react with aniline but smoothly reacted with aliphatic amines and benzylamine in moderate to good yield, fatty acids reacting with benzyl and aliphatic amines give amides in good to excellent yield. Chiral amino acids derivatives were transformed into amides without racemization in moderate yield. The possible mechanism of direct amidation catalyzed by TiCp2Cl2 was discussed. This catalytic method is very suitable for the amidation of low sterically hindered arylacetic acid, fatty acids with different low sterically hindered amines except aniline, as well as the amidation of aryl formic acid with benzyl and aliphatic amines.

A metal-free approach for the synthesis of amides/esters with pyridinium salts of phenacyl bromides via oxidative C–C bond cleavage

An efficient, simple, and metal-free synthetic approach for the N- and O-benzoylation of various amines/benzyl alcohols with pyridinium salts of phenacyl bromides is demonstrated to generate the corresponding amides and esters. This protocol facilitates the oxidative cleavage of a C–C bond followed by formation of a new C–N/C–O bond in the presence of K2CO3. Various pyridinium salts of phenacyl bromides can be readily transformed into a variety of amides and esters which is an alternative method for the conventional amidation and esterification in organic synthesis. High functional group tolerance, broad substrate scope and operational simplicity are the prominent advantages of the current protocol.

Base-promoted amide synthesis from aliphatic amines and ynones as acylation agents through C-C bond cleavage

A new protocol for the synthesis of amides via base-promoted cleavage of the C(sp)-C(CO) bond of ynones with aliphatic primary and secondary amines under transition-metal-, ligand-, and oxidant-free conditions has been developed. This method exhibits a wide substrate scope, high functional group tolerance and exclusive chemoselectivity, as well as mild reaction conditions.

Unmasking Amides: Ruthenium-Catalyzed Protodecarbonylation of N-Substituted Phthalimide Derivatives

The unprecedented transformation of a wide range of synthetically appealing phthalimides into amides in a single-step operation has been achieved in high yields and short reaction times using a ruthenium catalyst. Mechanistic studies revealed a unique, homogeneous pathway involving five-membered ring opening and CO2 release with water being the source of protons.