Chiral Amine Covalent Organic Cage Lingated with Copper for Asymmetric Decarboxylative Mannich Reaction

The efficient employment of chiral porous organic cages (POCs) for asymmetric catalysis is of great significance. In this work, we have synthesized a chiral N-rich organic cage constructed through chiral (<i>S</i>, <i>S</i>)-1,2-cyclohexanediamine and benzene-1,3,5-tricarbald...

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Bibliographic Details
Main Authors: Kaihong Liu, Chunxia Tan, Lingli Yuan
Format: Article
Language:English
Published: MDPI AG 2025-07-01
Series:Inorganics
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Online Access:https://www.mdpi.com/2304-6740/13/7/245
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Summary:The efficient employment of chiral porous organic cages (POCs) for asymmetric catalysis is of great significance. In this work, we have synthesized a chiral N-rich organic cage constructed through chiral (<i>S</i>, <i>S</i>)-1,2-cyclohexanediamine and benzene-1,3,5-tricarbaldehyde utilizing dynamic imine chemistry according to the literature. Following reduction with NaBH<sub>4</sub>, the resulting amine-based POCs (<b>RCC3</b>) feature appended chiral diamine moieties capable of coordinating Cu<sup>2+</sup> cations. This Cu<sup>2+</sup> coordination provides <b>RCC3</b> with excellent enantioselectivity as a supramolecular nanoreactor in asymmetric decarboxylative Mannich reactions, providing up to 94% ee of the product. We found that the spatial distribution of chiral amine sites and the coordination of Cu<sup>2+</sup> in the <b>RCC3</b> have a significant impact on catalytic activity, especially enantioselectivity. This work provides insights into the structure–function relationship within supramolecular catalytic systems
ISSN:2304-6740