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Computational Evidence for the Enamine Mechanism of Intramolecular Aldol Reactions Catalyzed by Proline

2004; Wiley; Volume: 43; Issue: 43 Linguagem: Inglês

10.1002/anie.200460916

1521-3773

Fernando R. Clemente, K. N. Houk,

Chemical Reaction Mechanisms

A comparison of previously proposed models of the CC bond-forming step of the title reaction with density functional methods indicate that the most favored one involves an enamine intermediate undergoing a concerted aldol cyclization with proton transfer from the proline carboxylic acid group (see structure). This step is equal in energy to the intramolecular deprotonation leading to the enamine, and both are partially rate-determining steps.