Wang Jing-Yi, Sun Jianwei
Department of Chemistry and the Hong Kong Branch of Chinese National Engineering Research Centre for Tissue Restoration & Reconstruction, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, 999077, Hong Kong SAR, China.
Angew Chem Int Ed Engl. 2025 Apr 7;64(15):e202424773. doi: 10.1002/anie.202424773. Epub 2025 Feb 11.
While modifications of the privileged catalyst backbones, such as 1,1'-spirobiindane-7,7'-diol (SPINOL), have led to the development of diverse useful chiral catalysts, the incorporation of heteroarenes in such chiral spirocyclic structures has limitedly known. Herein we report the design of a type of chiral spirocyclic bisindole skeletons where the electronically distinct heteroarenes serve as direct anchor for functional sites. Separate approaches for the synthesis of two different families of such skeletons have been developed via chiral phosphoric acid and rhodium catalysis, respectively. Both strategies provided expedient access to the highly enantioenriched spiro-bisindoles, owing to not only the high nucleophilicity of the indole ring, but also the robust asymmetric control. These new skeletons have been demonstrated as backbones of effective chiral catalysts for both transition metal catalysis and organocatalysis.
虽然对具有特殊结构的催化剂骨架进行修饰，如1,1'-螺二氢茚-7,7'-二醇（SPINOL），已促使多种有用的手性催化剂得以开发，但在这种手性螺环结构中引入杂芳烃的情况却鲜为人知。在此，我们报道了一种手性螺环双吲哚骨架的设计，其中电子性质不同的杂芳烃作为功能位点的直接锚定基团。分别通过手性磷酸和铑催化开发了两种不同类型的此类骨架的合成方法。这两种策略都能方便地获得高度对映体富集的螺双吲哚，这不仅是由于吲哚环的高亲核性，还得益于强大的不对称控制。这些新骨架已被证明是用于过渡金属催化和有机催化的有效手性催化剂的骨架。
