Construction of Axially Chiral Indoles by Cycloaddition–Isomerization via Atroposelective Phosphoric Acid and Silver Sequential Catalysis,ACS Catalysis

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Construction of Axially Chiral Indoles by Cycloaddition–Isomerization via Atroposelective Phosphoric Acid and Silver Sequential Catalysis
ACS Catalysis ( IF 11.3 ) Pub Date : 2022-06-22 , DOI: 10.1021/acscatal.2c02574
Yingcheng Wang ₁ , Xue Zhou ₁ , Wenyu Shan ₁ , Ruisong Liao ₁ , YuHua Deng ₁ , Fangzhi Peng ₁ , Zhihui Shao ₁

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Axially chiral indole-based frameworks occur in natural products, bioactive molecules, and chiral ligands. Thus, the development of catalytic asymmetric atroposelective approaches for de novo construction of these frameworks is highly valuable. Here, the atroposelective organo/metal combined dual catalysis strategy for de novo construction of valuable axially chiral indole frameworks has been developed. This protocol utilized a catalyst system of two chiral phosphoric acids (1 mol %) in combination with AgNO₃ (1 mol %) and was based on the unreported intermolecular cycloaddition–isomerization reaction of our recently introduced C-alkynyl N,O-acetals and 2-naphthylamines. An important class of hitherto inaccessible axially chiral indoles with a C–N axis were obtained in good yields and enantioselectivities. The axially chiral indoles obtained also provided a platform for the catalyst-controlled atroposelective synthesis of axially chiral indoles bearing two C–N axes, which are difficult to access by the existing methods. This work is also an example of 2-naphthylamines used as 1,3-dinucleophiles and three-atom (CCN) synthons in cycloadditions.

中文翻译：

环加成-异构化通过旋转选择性磷酸和银序列催化构建轴向手性吲哚

轴向手性吲哚基骨架存在于天然产物、生物活性分子和手性配体中。因此，开发用于从头构建这些框架的催化不对称阻转选择性方法是非常有价值的。在这里，已经开发了用于从头构建有价值的轴向手性吲哚骨架的阻转选择性有机/金属组合双催化策略。该协议使用了两种手性磷酸 (1 mol%) 与 AgNO _{3结合的催化剂体系}(1 mol %) 并且基于我们最近引入的 C-炔基 N,O-缩醛和 2-萘胺的未报道的分子间环加成 - 异构化反应。以良好的产率和对映选择性获得了一类重要的迄今为止难以获得的具有 C-N 轴的轴向手性吲哚。获得的轴向手性吲哚还为催化剂控制的介转选择性合成具有两个 C-N 轴的轴向手性吲哚提供了一个平台，这两个 C-N 轴是现有方法难以获得的。这项工作也是 2-萘胺在环加成反应中用作 1,3-双亲核试剂和三原子 (CCN) 合成子的一个例子。

更新日期：2022-06-22

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