원문정보
초록
영어
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(sp3) 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.
목차
1. Introduction
2. Synthetic Methods of Tertiary Acetamides
2.1. Tertiary Acetamide Synthesis in Organic Chemistry
2.2. Carbonylation of Tertiaryamine to Tertiary Amide by Transition Metal Complexes
3. Carbonylation of Trimethylamine with Methyl Iodide by Transition Metal Complexes
3.1. Role of Methyl Iodide and Its Regeneration from Tetramethylammonium Iodide
3.2. Carbonylation of Trimethylamine by Palladium Complexes
3.3. Carbonylation of Trimethylamine by Cobalt Complexes
3.4. Carbonylation of Quaternary Ammonium Salts by Cobalt Complex
3.5. Competitive Transference of Amino Moiety from Quarternary Ammonium Iodide to the Final Amide
3.6. Carbonylation of Trimethylamin by Rhodium Complex
4. Discussion
4.1. Generation of Methyl Iodide and Its Acylation
4.2. Generation of Alkyl Iodide and Its Carbonylation
4.3. Generation of Methyl Iodide and Its Hydrolysis
4.4. Generation of Acyl Iodide, Its Hydrolysis, and Its Amide Formation
4.5. Coordination of Trimethylamine to Transition Metals and Lewis Acid
4.6. The Formation of N,N-dimethylformamide and N-methylacetamide
4.7. Competitive Transference of Amino Moiety to the Final Amide Product during Carbonylation
5. Conculsions
Acknowledgments
References