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...
Saved in:
| Main Authors: | , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
MDPI AG
2025-07-01
|
| Series: | Inorganics |
| Subjects: | |
| Online Access: | https://www.mdpi.com/2304-6740/13/7/245 |
| Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
| _version_ | 1850076757840887808 |
|---|---|
| author | Kaihong Liu Chunxia Tan Lingli Yuan |
| author_facet | Kaihong Liu Chunxia Tan Lingli Yuan |
| author_sort | Kaihong Liu |
| collection | DOAJ |
| description | 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 |
| format | Article |
| id | doaj-art-c0d3ba23c21949efaee635a5f434ed50 |
| institution | DOAJ |
| issn | 2304-6740 |
| language | English |
| publishDate | 2025-07-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Inorganics |
| spelling | doaj-art-c0d3ba23c21949efaee635a5f434ed502025-08-20T02:45:56ZengMDPI AGInorganics2304-67402025-07-0113724510.3390/inorganics13070245Chiral Amine Covalent Organic Cage Lingated with Copper for Asymmetric Decarboxylative Mannich ReactionKaihong Liu0Chunxia Tan1Lingli Yuan2Department of Hematology, The Second Xiangya Hospital, Central South University, 139 Renmin Road, Changsha 410011, ChinaShanghai Frontiers Science Center of Biomimetic Catalysis, Joint Laboratory of International Cooperation of Resource Chemistry of Ministry of Education, Shanghai Normal University, Shanghai 200234, ChinaDepartment of Hematology, The Second Xiangya Hospital, Central South University, 139 Renmin Road, Changsha 410011, ChinaThe 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 systemshttps://www.mdpi.com/2304-6740/13/7/245covalent organic cagedecarboxylative Mannich reactionsasymmetric catalysis |
| spellingShingle | Kaihong Liu Chunxia Tan Lingli Yuan Chiral Amine Covalent Organic Cage Lingated with Copper for Asymmetric Decarboxylative Mannich Reaction Inorganics covalent organic cage decarboxylative Mannich reactions asymmetric catalysis |
| title | Chiral Amine Covalent Organic Cage Lingated with Copper for Asymmetric Decarboxylative Mannich Reaction |
| title_full | Chiral Amine Covalent Organic Cage Lingated with Copper for Asymmetric Decarboxylative Mannich Reaction |
| title_fullStr | Chiral Amine Covalent Organic Cage Lingated with Copper for Asymmetric Decarboxylative Mannich Reaction |
| title_full_unstemmed | Chiral Amine Covalent Organic Cage Lingated with Copper for Asymmetric Decarboxylative Mannich Reaction |
| title_short | Chiral Amine Covalent Organic Cage Lingated with Copper for Asymmetric Decarboxylative Mannich Reaction |
| title_sort | chiral amine covalent organic cage lingated with copper for asymmetric decarboxylative mannich reaction |
| topic | covalent organic cage decarboxylative Mannich reactions asymmetric catalysis |
| url | https://www.mdpi.com/2304-6740/13/7/245 |
| work_keys_str_mv | AT kaihongliu chiralaminecovalentorganiccagelingatedwithcopperforasymmetricdecarboxylativemannichreaction AT chunxiatan chiralaminecovalentorganiccagelingatedwithcopperforasymmetricdecarboxylativemannichreaction AT lingliyuan chiralaminecovalentorganiccagelingatedwithcopperforasymmetricdecarboxylativemannichreaction |