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http://dx.doi.org/10.13160/ricns.2017.10.4.175

Syntheses of Amide Bonds and Activations of N-C(sp3) Bonds  

Hong, Jang-Hwan (Department of Nanopolymer Material Engineering, Pai Chai University)
Publication Information
Journal of Integrative Natural Science / v.10, no.4, 2017 , pp. 175-191 More about this Journal
Abstract
In organic chemistry amide synthesis is performed through condensation of a carboxylic acid and an amine with releasing one equivalent of water via the corresponding ammonium carboxylate salt. This method is suffering from tedious processes and poor atom-economy due to the adverse thermodynamics of the equilibrium and the high activation barrier for direct coupling of a carboxylic acid and an amine. Most of the chemical approaches to amides formations have been therefore being developed, they are mainly focused on secondary amides. Direct carbonylations of tertiary amines to amides have been an exotic field unresolved, in particular direct carbonylation of trimethylamine in lack of commercial need has been attracted much interests due to the versatile product of N,N-dimethylacetamide in chemical industries and the activation of robust N-C($sp^3$) bond in tertiary amine academically. This review is focused mainly on carbonylation of trimethylamine as one of the typical tertiary amines by transition metals of cobalt, rhodium, platinum, and palladium including the role of methyl iodide as a promoter, the intermediate formation of acyl iodide, the coordination ability of trimethylamine to transition metal catalysts, and any possibility of CO insertion into the bond of Me-N in trimethylamine. In addition reactions of acyl halides as an activated form of acetic acid with amines are reviewed in brief since acyl iodide is suggested as a critical intermediate in those carbonylations of trimethylamine.
Keywords
Carbonylation; Tertiary Amine; Tertiary Amide; Trimethylamine; Dimethylacetamide; Intramolecular; Acyl iodide; Methyl iodide; Quaternary Ammonium Iodide;
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