Regiodivergent Ring Opening of Chiral Aziridines
Regiodivergent Ring Opening of Chiral Aziridines
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DOI：
10.1126/science.1180739
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发表时间：
2009-12-18
期刊：
影响因子：
56.9
通讯作者：
RajanBabu, T. V.
中科院分区：
文献类型：
--
作者：
Wu, Bin;Parquette, Jon R.;RajanBabu, T. V.
已证明，应变三元环的动力学拆分对于生成对映体纯有机中间体具有广泛的用途。在此，我们展示了一种补充方法，通过单一催化剂将氮丙啶的外消旋混合物转化为一对区域异构产物，每种产物均具有良好的产率和极高的对映选择性。具体而言，二聚钇 salen 催化剂通过三甲基甲硅烷基叠氮化物加速脂肪族氮丙啶的开环，从而诱导一种对映体的伯位和另一种对映体的仲位的亲核攻击。速率和选择性对催化剂结构高度敏感。
Kinetic resolution of strained three-membered rings has proven broadly useful for the generation of enantiopure organic intermediates. Herein we demonstrate a complementary approach whereby a single catalyst transforms a racemic mixture of aziridines to a pair of regioisomeric products, each in good yield with exceptionally high enantioselectivity. Specifically, the dimeric yttrium salen catalyst accelerates the ring opening of aliphatic aziridines by trimethylsilylazide, inducing nucleophilic attack at the primary position of one enantiomer and the secondary position of the other. Both rate and selectivity are highly sensitive to the catalyst structure.