The preference for anti over Gauche migration in the Baeyer-Villiger reaction |
| |
Authors: | Snowden Michelle Bermudez Amy Kelly David R Radkiewicz-Poutsma Jennifer L |
| |
Institution: | Department of Chemistry and Biochemistry, Old Dominion University, 4541 Hampton Boulevard, Norfolk, Virginia 20529, USA. |
| |
Abstract: | 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. |
| |
Keywords: | |
本文献已被 PubMed 等数据库收录! |
|