99071-56-4

Upstream product

• 79-16-3 N-methyl-acetamide 
• 623-00-7 4-bromobenzenecarbonitrile 
• 35704-19-9 N-(4-cyanophenyl)acetamide 
• 74-88-4 methyl iodide 
• 121-95-9 N-methyl-4-nitroacetanilide 
• 108-24-7 acetic anhydride 
• 1197-19-9 4-cyano-N,N-dimethylaniline 
• 75-91-2 tert.-butylhydroperoxide 
• 201230-82-2 carbon monoxide 
• 579-10-2 N-acetyl-N-methylaniline 
• 119-63-1 4-(N-methylacetamido)aniline 
• 151-50-8 potassium cyanide 
• 50438-47-6 N-(4-bromo-phenyl)-N-methylacetamide 
• 873-74-5 4-Aminobenzonitrile 

Downstream Products

• 4714-62-9 4-cyano-N-methylaniline 
• 806632-62-2 4-methylamino-benzamidine 
• 579-10-2 N-acetyl-N-methylaniline 

Relevant academic research and scientific papers

Carbonylation of C?N Bonds in Tertiary Amines Catalyzed by Low-Valent Iron Catalysts

The first iron catalysts able to promote the formal insertion of CO into the C?N bond of amines are reported. Using low-valent iron complexes, including K2[Fe(CO)4], amides are formed from aromatic and aliphatic amines, in the presence of an iodoalkane promoter. Inorganic Lewis acids, such as AlCl3 and Nd(OTf)3, have a positive influence on the catalytic activity of the iron salts, enabling the carbonylation at a low pressure of CO (6 to 8 bars).

The copper-catalyzed aerobic oxidative amidation of tertiary amines

A general and efficient method for the synthesis of tertiary amides has been developed via the copper-catalyzed aerobic oxidative amidation of tertiary amines. Due to the use of the O2 oxidant, various functional groups were well tolerated under the present conditions. Extensive substrates studies demonstrated its potential as a practical approach for the synthesis of tertiary amides.

Amide bond formation through iron-catalyzed oxidative amidation of tertiary amines with anhydrides

A general and efficient method for amide bond synthesis has been developed. The method allows for synthesis of tertiary amides from readily available tertiary amines and anhydrides in the presence of FeCl2 as catalyst and tert-butyl hydroperoxide in water (T-Hydro) as oxidant. Mechanistic studies indicated that the in situ-generated α-amino peroxide of tertiary amine and iminium ion act as key intermediates in this oxidative transformation.

Amide conformational switching induced by protonation of aromatic substituent

(Matrix presented) Introduction of an electron-withdrawing group on the aromatic ring of N-methylacetanilide decreased the ratio of the cis conformer, and the ratio correlates well with the Hammett σ values of the substituents. These steric properties can be applied to achieve amide conformational swiching by protonation at the aromatic substituent of 4-[bis(dimethylamino)]-N-methylacetanilide or N-[p-(dimethylamino)phenyl]-N-phenylacetamide.

Pd-catalyzed intermolecular amidation of aryl halides: The discovery that xantphos can be trans-chelating in a palladium complex

A general method for the intermolecular coupling of aryl halides and amides using a Xantphos/ Pd catalyst is described. This system displays good functional group compatibility, and the desired C-N bond forming process proceeds in good to excellent yields with 1-4 mol % of the Pd catalyst. Additionally, the arylation of sulfonamides, oxazolidinones, and ureas is reported. The efficiency of these transformations was found to be highly dependent on reaction concentrations and catalyst loadings. A Pd complex resulting from oxidative addition of 4-bromobenzonitrile, (Xantphos)Pd(4-cyanophenyl)(Br) (II), was prepared in one step from Xantphos, Pd2(dba)3, and the aryl bromide. Complex II proved to be an active catalyst for the coupling between 4-bromobenzonitrile and benzamide. X-ray crystallographic analysis of II revealed a rare trans-chelating bisphosphine-Pd(II) structure with a large bite angle of 150.7°.

Palladium-catalyzed intermolecular coupling of aryl halides and amides

The first general intermolecular C-N bond-forming reactions between aryl halides and amides were realized using a palladium catalyst with Xantphos as the ligand. Aryl triflates, carbamates, and sulfonamides are also viable substrates for the amidations, which proceed at 45-110 °C with 1-4 mol% of Pd catalyst in 66-99% yields and exhibit good functional group compatibility.