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

被引：22
作者：
Snowden, M
Bermudez, A
Kelly, DR
Radkiewicz-Poutsma, JL
机构：
[1] Old Dominion Univ, Dept Chem & Biochem, Norfolk, VA 20529 USA
[2] Cardiff Univ, Sch Chem, Cardiff CF10 3TB, S Glam, Wales
来源：
JOURNAL OF ORGANIC CHEMISTRY | 2004年 / 69卷 / 21期
关键词：
D O I：
10.1021/jo0491307
中图分类号：
O62 [有机化学];
学科分类号：
070303 ; 081704 ;
摘要：
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 A 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.
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收藏
页码：7148 / 7156
页数：9
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