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Ab initio study of catalyzed and uncatalyzed amide bond formation as a model for peptide bond formation: Ammonia-Glycine reactions

✍ Scribed by Tetsuro Oie; Gilda H. Loew; Stanley K. Burt; Robert D. Macelroy


Publisher
John Wiley and Sons
Year
1983
Tongue
English
Volume
4
Category
Article
ISSN
0192-8651

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✦ Synopsis


As a model reaction for peptide and bond formation, the s N 2 reactions between glycine and ammonia have been studied with and without amine catalysis:

using ab initio molecular-orbital methods. For each of the catalyzed and uncatalyzed reactions, two reaction mechanisms have been examined: a two-step and a concerted mechanism. The stationary points of each reaction, including intermediate and transition states, have been identified and free energies calculated for all geometry-optimized reaction species to determine the thermodynamics and kinetics of the reaction. The calculations demonstrate that a second ammonia molecule catalyzes amide bond formation, and that the two-step mechanism is more favorable than the concerted one for the catalyzed reaction, while for the uncatalyzed reaction both mechanisms are competitive.