Theoretical Insight into the Mechanism of an Efficient ʟ-Proline-catalyzed Transamidation of Acetamide with Benzylamine

Abstract

The detailed mechanisms of the efficient L-proline and pyrrolidine catalyzed transamidation of acetamide with benzylamine have been investigated using density functional theory (DFT) calculations. Our calculated results show: (1) the mechanisms of two catalytic cycle reactions are similar. However, the rate-determining steps of their reactions are different for the whole catalytic process. One is the intramolecular nucleophilic addition reaction of 1-COM, the other is hydrolysis reaction of 2-C. (2) COOH group of L-proline is essential for efficient transamidation. The computational results are in good agreement withthe experiment finding and mechanism resported by Rao et al. for L-proline-catalyzed synthesis of amidesin good to excellent yields.

Transamidation vitrimers enabled by neighbouring fluorine atom activation

“…The computations used the same methodology (functional, basis sets and various corrections, see details in the Experimental section) as our previously published study of the F substitution effect on the transesterification rate. 78 The literature reports only a few DFT investigations of the transamidation reaction mechanism, mostly restricted to metalcatalyzed 53,82,83 or organocatalyzed [84][85][86] processes. It seems that only one report has addressed the non-catalyzed transamidation of a special amide (RCO-NMeOMe, a "Weinreb" amide), in comparison with the CO 2 -catalyzed process.…”