Pd-Catalyzed Asymmetric Allylic Substitution Annulation Using Enolizable Ketimines as Nucleophiles: An Alternative Approach to Chiral Tetrahydroindoles
Pd-Catalyzed Asymmetric Allylic Substitution Annulation Using Enolizable Ketimines as Nucleophiles: An Alternative Approach to Chiral Tetrahydroindoles
复制标题
使用烯醇化酮亚胺作为亲核试剂的 Pd 催化不对称烯丙基取代环化：手性四氢吲哚的替代方法
DOI：
10.1002/adsc.202000151
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发表时间：
2020
影响因子：
5.4
通讯作者：
Zhang Wanbin
中科院分区：
文献类型：
--
作者：
Xu Kai;Ye Jianxun;Liu Hao;Shen Jiefeng;Liu Delong;Zhang Wanbin
以不稳定的烯醇化酮亚胺为亲核剂，以我们先前开发的Bu-RuPhOx为手性配体，通过钯催化的不对称烯丙基取代环化反应合成了手性四氢吲哚类化合物。反应通过不对称去对称反应进行，以中等到良好的产率提供了所需的手性四氢吲哚，ee高达96%。环化反应可以高产率地在克级规模上进行，产物可以转化为几种类型的N-杂双环衍生物。此外，以手性四氢吲哚为起始原料，还合成了手性全氢吲哚酸衍生物。
A synthesis of chiral tetrahydroindoles has been developed via a Pd‐catalyzed asymmetric allylic substitution annulation using unstable enolizable ketimines as nucleophiles and our previously developedtBu‐RuPHOX as a chiral ligand. The reaction proceeds via an asymmetric desymmetrization of themeso‐diacetatecycloalkenes, providing the desired chiral tetrahydroindoles in moderate to good yields and with up to 96% ee. The annulation reaction could be performed on a gram‐scale in high yields and the resulting products can be transformed to several types ofN‐hetereobicyclic derivatives. In addition, a chiralcis‐perhydroindolic acid derivative was also readily synthesized starting from a prepared chiral tetrahydroindole.