Fast racemisation and slow epimerisation of laterally lithiated amides: stereochemical evidence for the mechanism of inversion of amide-substituted benzyllithiums
Fast racemisation and slow epimerisation of laterally lithiated amides: stereochemical evidence for the mechanism of inversion of amide-substituted benzyllithiums
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DOI：
10.1039/b310963a
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发表时间：
2004-01-21
影响因子：
4.9
通讯作者：
Wheatley, AEH
中科院分区：
文献类型：
--
作者：
Clayden, J;Stimson, CC;Wheatley, AEH
叔1-萘酰胺外消旋慢得多，比他们的横向锂化衍生物，和这些衍生物的外消旋和差向异构化的相对速率表明，锂轴承立体异构中心反转通过“进行巡回”机制，其中锂阳离子是从一个面传递到另一个通过协调旋转酰胺基团。
Tertiary 1-naphthamides racemise much more slowly than their laterally lithiated derivatives, and the relative rates of racemisation and epimerisation of these derivatives indicate that the lithium-bearing stereogenic centre inverts via a "conducted tour" mechanism, in which the lithium cation is delivered from one face to the other by coordination to the rotating amide group.