Thermo-responsive chiral micelles as recyclable organocatalyst for asymmetric Rauhut-Currier reaction in water
Abstract Developing eco-friendly chiral organocatalysts with the combined advantages of homogeneous catalysis and heterogeneous processes is greatly desired. In this work, a family of amphiphilic one-handed helical polyisocyanides bearing phosphine pendants is prepared, which self-assembles into wel...
| Main Authors: | , , , , , , |
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| Format: | Article |
| Language: | English |
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Nature Portfolio
2023-11-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-023-43092-7 |
| _version_ | 1797630135859412992 |
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| author | Lei Xu Li Zhou Yan-Xiang Li Run-Tan Gao Zheng Chen Na Liu Zong-Quan Wu |
| author_facet | Lei Xu Li Zhou Yan-Xiang Li Run-Tan Gao Zheng Chen Na Liu Zong-Quan Wu |
| author_sort | Lei Xu |
| collection | DOAJ |
| description | Abstract Developing eco-friendly chiral organocatalysts with the combined advantages of homogeneous catalysis and heterogeneous processes is greatly desired. In this work, a family of amphiphilic one-handed helical polyisocyanides bearing phosphine pendants is prepared, which self-assembles into well-defined chiral micelles in water and showed thermo-responsiveness with a cloud point of approximately 38.4 °C. The micelles with abundant phosphine moieties at the interior efficiently catalyze asymmetric cross Rauhut-Currier reaction in water. Various water-insoluble substrates are transferred to target products in high yield with excellent enantioselectivity. The yield and enantiomeric excess (ee) of the product generated in water are up to 90% and 96%, respectively. Meanwhile, the yields of the same R-C reaction catalyzed by the polymer itself in organic solvents is <16%, with an ee < 72%. The homogeneous reaction of the chiral micelles in water turns to heterogeneous at temperatures higher than the cloud point, and the catalyst precipitation facilitates product isolation and catalyst recovery. The polymer catalyst is recycled 10 times while maintaining activity and enantioselectivity. |
| first_indexed | 2024-03-11T11:03:45Z |
| format | Article |
| id | doaj.art-dbede2cc03474edd96a2873e40744c2b |
| institution | Directory Open Access Journal |
| issn | 2041-1723 |
| language | English |
| last_indexed | 2024-03-11T11:03:45Z |
| publishDate | 2023-11-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj.art-dbede2cc03474edd96a2873e40744c2b2023-11-12T12:23:35ZengNature PortfolioNature Communications2041-17232023-11-0114111010.1038/s41467-023-43092-7Thermo-responsive chiral micelles as recyclable organocatalyst for asymmetric Rauhut-Currier reaction in waterLei Xu0Li Zhou1Yan-Xiang Li2Run-Tan Gao3Zheng Chen4Na Liu5Zong-Quan Wu6State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin UniversityDepartment of Polymer Science and Engineering, Hefei University of TechnologyDepartment of Polymer Science and Engineering, Hefei University of TechnologyState Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin UniversityState Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin UniversityThe School of Pharmaceutical Sciences, Jilin UniversityState Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin UniversityAbstract Developing eco-friendly chiral organocatalysts with the combined advantages of homogeneous catalysis and heterogeneous processes is greatly desired. In this work, a family of amphiphilic one-handed helical polyisocyanides bearing phosphine pendants is prepared, which self-assembles into well-defined chiral micelles in water and showed thermo-responsiveness with a cloud point of approximately 38.4 °C. The micelles with abundant phosphine moieties at the interior efficiently catalyze asymmetric cross Rauhut-Currier reaction in water. Various water-insoluble substrates are transferred to target products in high yield with excellent enantioselectivity. The yield and enantiomeric excess (ee) of the product generated in water are up to 90% and 96%, respectively. Meanwhile, the yields of the same R-C reaction catalyzed by the polymer itself in organic solvents is <16%, with an ee < 72%. The homogeneous reaction of the chiral micelles in water turns to heterogeneous at temperatures higher than the cloud point, and the catalyst precipitation facilitates product isolation and catalyst recovery. The polymer catalyst is recycled 10 times while maintaining activity and enantioselectivity.https://doi.org/10.1038/s41467-023-43092-7 |
| spellingShingle | Lei Xu Li Zhou Yan-Xiang Li Run-Tan Gao Zheng Chen Na Liu Zong-Quan Wu Thermo-responsive chiral micelles as recyclable organocatalyst for asymmetric Rauhut-Currier reaction in water Nature Communications |
| title | Thermo-responsive chiral micelles as recyclable organocatalyst for asymmetric Rauhut-Currier reaction in water |
| title_full | Thermo-responsive chiral micelles as recyclable organocatalyst for asymmetric Rauhut-Currier reaction in water |
| title_fullStr | Thermo-responsive chiral micelles as recyclable organocatalyst for asymmetric Rauhut-Currier reaction in water |
| title_full_unstemmed | Thermo-responsive chiral micelles as recyclable organocatalyst for asymmetric Rauhut-Currier reaction in water |
| title_short | Thermo-responsive chiral micelles as recyclable organocatalyst for asymmetric Rauhut-Currier reaction in water |
| title_sort | thermo responsive chiral micelles as recyclable organocatalyst for asymmetric rauhut currier reaction in water |
| url | https://doi.org/10.1038/s41467-023-43092-7 |
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