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The preference for anti over gauche migration in the Baeyer-Villiger reaction

Journal of Organic Chemistry, ISSN: 0022-3263, Vol: 69, Issue: 21, Page: 7148-7156
2004
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Article Description

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.

Bibliographic Details

Snowden, Michelle; Bermudez, Amy; Kelly, David R; Radkiewicz-Poutsma, Jennifer L

American Chemical Society (ACS)

Chemistry

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