ENANTIOSELECTIVE SYNTHESIS VIA SPARTEINE-INDUCED ASYMMETRIC DEPROTONATION
ENANTIOSELECTIVE SYNTHESIS VIA SPARTEINE-INDUCED ASYMMETRIC DEPROTONATION
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DOI：
10.1351/pac199466071479
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发表时间：
1994-07-01
影响因子：
1.8
通讯作者：
HOPPE, I
中科院分区：
文献类型：
--
作者：
HOPPE, D;HINTZE, F;HOPPE, I
非手性氨基甲酸酯与仲丁基锂/(-)-sparteine的脱质子反应在与亲电试剂反应后发生脱保护后，以高度手性识别生成ee大于或等于95%的取代醇。立体选择由动力学控制，并提出了定性过渡态模型。本文报道了立体氨基甲酸烷基酯对映体的判别及其在动力学分辨中的应用。对外部竞争和内部竞争的研究较少。-最后，我们披露了1-亚甲基的对映选择性亲电取代的简短报告；在这里，立体选择的起源是热力学驱动的非对映异构体独立基-锂sparteine配合物的外映作用。
The deprotonation of achiral alkyl carbamates with sec-butyllithium/(-)-sparteine proceeds with a high degree of chiral recognition to form substituted alcohols usually with greater-than-or-equal-to 95 % ee after reaction with electrophiles followed by deprotection. The stereoselection is kinetically controlled and a qualitative transition state model is proposed. Some studies, concerning the discrimination between both enantiomers of stereogenic alkyl carbamates and on its utilization for the kinetic resolution are reported. The competition between external and internal competition was investigated in few cases. - Finally, we disclose a short report on the enantioselective electrophilic substitution of 1-methylindene; here the origin of stereoselection is an thermodynamically driven epimerization of diastereomeric indenyl-lithium sparteine complexes.