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Theoretical Investigation of the Mechanism of the Baeyer‐Villiger Reaction in Nonpolar Solvents
Author(s) -
Okuno Yoshishige
Publication year - 1997
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.19970030208
Subject(s) - chemistry , kinetic isotope effect , catalysis , autocatalysis , acetic acid , trifluoroacetic acid , reaction mechanism , substituent , photochemistry , aldehyde , rate determining step , benzaldehyde , reaction rate , medicinal chemistry , acid catalysis , organic chemistry , computational chemistry , deuterium , physics , quantum mechanics
The Baeyer‐Villiger reaction of p ‐anisaldehyde with peroxyacetic acid in nonpolar solvents to give p ‐anisylformate was examined on the basis of ab initio molecular orbital calculations. To explain the experimental observations, the free‐energy change was evaluated for each case in the absence and in the presence of an acid catalyst. It was found that, without catalysts, the rate‐determining step corresponds to the carbonyl addition of peroxyacetic acid to p ‐anisaldehyde and the reaction hardly occurs. Acetic acid was found to catalyze the carbonyl addition and change the rate‐determining step from the carbonyl addition to the migration of the carbonyl‐adduct intermediate. Trifluoroacetic acid was observed to catalyze both the carbonyl addition and migration, and the carbonyl addition was demonstrated to be a rate‐determining step. The results provided a convincing explanation of the complex kinetics seen experimentally. Further calculations were performed for the reaction of benzaldehyde with peroxyacetic acid to give phenylformate. Migratory aptitude was found to depend on the catalyst. Isotope effects were also investigated, and the exceptional isotope effect observed experimentally was shown to be due to the rate‐determining carbonyl addition caused by autocatalysis. It is concluded that the mechanism of the reaction varies with catalysis or substituent effects.