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Computational Evidence for the Enamine Mechanism of Intramolecular Aldol Reactions Catalyzed by Proline
Author(s) -
Clemente Fernando R.,
Houk K. N.
Publication year - 2004
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.200460916
Subject(s) - enamine , aldol reaction , intramolecular force , chemistry , deprotonation , organocatalysis , proline , catalysis , stereochemistry , organic chemistry , enantioselective synthesis , amino acid , biochemistry , ion
A comparison of previously proposed models of the CC 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.