The Preference for Anti over Gauche Migration in the Baeyer−Villiger Reaction

Explanations for stereoselectivity in the Baeyer−Villiger reaction have relied on the assumption that the antiperiplanar (app) group migrates. However, the magnitude of the preference for app-migration over gauche migration is unknown. To investigate this, the energy differences between the two were...

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Bibliographic Details
Published in:Journal of organic chemistry 2004-10, Vol.69 (21), p.7148-7156
Main Authors: Snowden, Michelle, Bermudez, Amy, Kelly, David R, Radkiewicz-Poutsma, Jennifer L
Format: Article
Language:English
Subjects:
Chemistry
Cyclization
Exact sciences and technology
Ketones - chemistry
Kinetics and mechanisms
Models, Molecular
Molecular Conformation
Organic chemistry
Oxidation-Reduction
Reactivity and mechanisms
Stereoisomerism
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Summary:Explanations for stereoselectivity in the Baeyer−Villiger reaction have relied on the assumption that the antiperiplanar (app) group migrates. However, the magnitude of the preference for app-migration over gauche migration is unknown. To investigate this, the energy differences between the two were estimated from ab initio calculations. App-migration was found to be the preferred pathway since no transition structure could be located for gauche migration. Barriers for gauche migration were estimated by performing constrained optimizations. App-migration was found to be strongly favored with a barrier that is at least 3.8 kcal/mol and as much as 58.0 kcal/mol lower in energy than the gauche migration barrier.
ISSN:0022-3263
1520-6904
DOI:10.1021/jo0491307