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 developed ^tBu‐RuPHOX as a chiral ligand. The reaction proceeds via an asymmetric desymmetrization of the meso‐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 of N‐hetereobicyclic derivatives. In addition, a chiral cis‐perhydroindolic acid derivative was also readily synthesized starting from a prepared chiral tetrahydroindole.

中文翻译：

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Pd催化的不对称烯丙基取代环化使用可烯化的酮亚胺作为亲核试剂：手性四氢吲哚的另一种方法

手性四氢吲哚的合成是通过使用不稳定的可烯醇化酮亚胺作为亲核试剂，以及我们先前开发的^t Bu-RuPHOX作为手性配体，通过Pd催化的不对称烯丙基取代环进行的。反应通过内消旋二乙酸双环烯烃的不对称脱对称进行，以中等至良好的收率提供了所需的手性四氢吲哚，且ee高达96％。环化反应可以以克级进行，且收率很高，并且可以将生成的产物转化为多种类型的N杂环双环衍生物。此外，从制备的手性四氢吲哚开始，也很容易合成手性顺式-全氢吲哚酸衍生物。