Dynamic kinetic resolution during a cascade reaction on substrates with chiral all-carbon quaternary centers.
Dynamic kinetic resolution during a cascade reaction on substrates with chiral all-carbon quaternary centers.
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DOI：
10.1002/anie.200462039
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发表时间：
2005-04
影响因子：
--
通讯作者：
K. Xu;G. Lalic;S. Sheehan;M. Shair
中科院分区：
文献类型：
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作者：
K. Xu;G. Lalic;S. Sheehan;M. Shair
动态动力学拆分已成为有机化合物非对映选择性和对映选择性合成的一种有效方法。[1]动态动力学拆分，如方程式（1）（方案1）所示，以其最常见的形式，导致立体异构体的混合物转化为富含一种对映异构体或非对映异构体的产物的转化率大于50%。[2]大多数动态动力学拆分需要快速平衡的对映体起始材料，其经历较慢的第二步，其中对映体与对映体富集的试剂以不同的速率反应（k1 R/46 k1 S;方案1，Eq.① ①）。从概念上讲，很难想象不直接对映异构化敏感的起始材料，例如其中唯一手性存在于全碳季立体中心中的分子，如何参与动态动力学拆分。然而，如果不能直接对映异构化的分子经历级联反应（包括一个或多个间-对映异构化的反应），则可以将其转化为对映异构体。
Dynamic kinetic resolution has become a useful method for the diastereoselective and enantioselective synthesis of organic compounds.[1] Dynamic kinetic resolution, presented in Equation (1)(Scheme 1), in its most common form results in greater than 50% conversion of a mixture of stereoisomers into products enriched in one enantiomer or diastereoisomer.[2]Most dynamic kinetic resolutions require rapidly equilibrating enantiomeric starting materials that undergo a slower second step, in which the enantiomers react with enantiomerically enriched reagents at different rates (k1R ¼6k1S; Scheme 1, Eq.(1)). Conceptually, it is difficult to imagine how starting materials that are not directly susceptible to enantiomerization, such as molecules where the only chirality present is in all-carbon quaternary stereocenters, could take part in dynamic kinetic resolutions. However, if a molecule incapable of direct enantiomerization were to undergo a cascade reaction (a reaction comprising one or more inter-