No abstract

This work describes a highly efficient unstrained C(sp 3 )-N bond activation approach for synthesis of N,N-dimethylacetamide (DMAc) via catalytic carbonylation of trimethylamine using a PdCl 2 /bipy (bipy = 2,2 0 -bipyridine)/Me 4 NI catalyst system. A low Pd catalyst dosage (1.0 mol%) is sufficient for high selectivity (98.1%) and yield (90.8%), with a turnover number (TON) of 90.0 mmol of DMAc obtained per mmol of PdCl 2 employed under mild reaction conditions. The influence of reaction parameters such as catalyst precursor dosage, ligand type and promoter on activity is investigated. This work also discusses in detail the halide promoter's role in the reaction, and provides a plausible mechanism based on the intermediates methyl iodide and acetyl iodide. Analyses indicate that the carbonylation of trimethylamine may proceed through an active intermediate acetyl iodide formed by carbonylation of methyl iodide generated from the decomposition of the promoter Me 4 NI under reaction conditions. The formation of acetyl iodide favors the cleaving efficiency of the inert unstrained C(sp 3 )-N bond of trimethylamine.

This work describes a mild and efficient approach for the synthesis of aryl amides via catalytic aminocarbonylation of aryl halides with alicyclic amines using a Pd (P t Bu 3 ) 2 /NH 4 Cl catalyst system. Under mild reaction temperature of 60°C and balloon pressure of CO, 5 mol% Pd(P t Bu 3 ) 2 with a cheap NH 4 Cl promoter is sufficient for high yields of aryl amides. The influence of reaction parameters such as reaction temperature, ligand type and promoter on catalytic activity was investigated. This work also discusses the catalytic intermediates in detail, and provides a plausible mechanism based on an acid chloride intermediate.

No abstract