Enantioselective synthesis of inherently chiral sulfur-containing calix[4]arenes via chiral sulfide catalyzed desymmetrizing aromatic sulfenylation
Abstract Inherently chiral calixarenes hold great potential for applications in chiral recognition, sensing, and asymmetric catalysis due to their unique structures. However, due to their special structures and relatively large sizes, the catalytic asymmetric synthesis of inherently chiral calixaren...
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| Format: | Article |
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Nature Portfolio
2024-11-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-024-54380-1 |
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| author | Xin-Yu Zhang Deng Zhu Ren-Fei Cao Yu-Xuan Huo Tong-Mei Ding Zhi-Min Chen |
| author_facet | Xin-Yu Zhang Deng Zhu Ren-Fei Cao Yu-Xuan Huo Tong-Mei Ding Zhi-Min Chen |
| author_sort | Xin-Yu Zhang |
| collection | DOAJ |
| description | Abstract Inherently chiral calixarenes hold great potential for applications in chiral recognition, sensing, and asymmetric catalysis due to their unique structures. However, due to their special structures and relatively large sizes, the catalytic asymmetric synthesis of inherently chiral calixarenes is challenging with very limited examples available. Here, we present an efficient method for the enantioselective synthesis of inherently chiral sulfur-containing calix[4]arenes through the desymmetrizing electrophilic sulfenylation of calix[4]arenes. This catalytic asymmetric reaction is enabled by a chiral 1,1’-binaphthyl-2,2’-diamine-derived sulfide catalyst and hexafluoroisopropanol. Various inherently chiral sulfur-containing calix[4]arenes are obtained in moderate to excellent yields with high enantioselectivities. Control experiments indicate that the thermodynamically favored C-SAr product is formed from the kinetically favored N-SAr product and the combination of the chiral sulfide catalyst and hexafluoroisopropanol is crucially important for both enantioselectivity and reactivity. |
| format | Article |
| id | doaj-art-d87e223871f74aadbef4c823023b2f9c |
| institution | Kabale University |
| issn | 2041-1723 |
| language | English |
| publishDate | 2024-11-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj-art-d87e223871f74aadbef4c823023b2f9c2024-11-17T12:37:26ZengNature PortfolioNature Communications2041-17232024-11-0115111010.1038/s41467-024-54380-1Enantioselective synthesis of inherently chiral sulfur-containing calix[4]arenes via chiral sulfide catalyzed desymmetrizing aromatic sulfenylationXin-Yu Zhang0Deng Zhu1Ren-Fei Cao2Yu-Xuan Huo3Tong-Mei Ding4Zhi-Min Chen5School of Chemistry and Chemical Engineering, Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, Shanghai Jiao Tong UniversitySchool of Chemistry and Chemical Engineering, Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, Shanghai Jiao Tong UniversitySchool of Chemistry and Chemical Engineering, Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, Shanghai Jiao Tong UniversitySchool of Chemistry and Chemical Engineering, Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, Shanghai Jiao Tong UniversitySchool of Chemistry and Chemical Engineering, Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, Shanghai Jiao Tong UniversitySchool of Chemistry and Chemical Engineering, Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, Shanghai Jiao Tong UniversityAbstract Inherently chiral calixarenes hold great potential for applications in chiral recognition, sensing, and asymmetric catalysis due to their unique structures. However, due to their special structures and relatively large sizes, the catalytic asymmetric synthesis of inherently chiral calixarenes is challenging with very limited examples available. Here, we present an efficient method for the enantioselective synthesis of inherently chiral sulfur-containing calix[4]arenes through the desymmetrizing electrophilic sulfenylation of calix[4]arenes. This catalytic asymmetric reaction is enabled by a chiral 1,1’-binaphthyl-2,2’-diamine-derived sulfide catalyst and hexafluoroisopropanol. Various inherently chiral sulfur-containing calix[4]arenes are obtained in moderate to excellent yields with high enantioselectivities. Control experiments indicate that the thermodynamically favored C-SAr product is formed from the kinetically favored N-SAr product and the combination of the chiral sulfide catalyst and hexafluoroisopropanol is crucially important for both enantioselectivity and reactivity.https://doi.org/10.1038/s41467-024-54380-1 |
| spellingShingle | Xin-Yu Zhang Deng Zhu Ren-Fei Cao Yu-Xuan Huo Tong-Mei Ding Zhi-Min Chen Enantioselective synthesis of inherently chiral sulfur-containing calix[4]arenes via chiral sulfide catalyzed desymmetrizing aromatic sulfenylation Nature Communications |
| title | Enantioselective synthesis of inherently chiral sulfur-containing calix[4]arenes via chiral sulfide catalyzed desymmetrizing aromatic sulfenylation |
| title_full | Enantioselective synthesis of inherently chiral sulfur-containing calix[4]arenes via chiral sulfide catalyzed desymmetrizing aromatic sulfenylation |
| title_fullStr | Enantioselective synthesis of inherently chiral sulfur-containing calix[4]arenes via chiral sulfide catalyzed desymmetrizing aromatic sulfenylation |
| title_full_unstemmed | Enantioselective synthesis of inherently chiral sulfur-containing calix[4]arenes via chiral sulfide catalyzed desymmetrizing aromatic sulfenylation |
| title_short | Enantioselective synthesis of inherently chiral sulfur-containing calix[4]arenes via chiral sulfide catalyzed desymmetrizing aromatic sulfenylation |
| title_sort | enantioselective synthesis of inherently chiral sulfur containing calix 4 arenes via chiral sulfide catalyzed desymmetrizing aromatic sulfenylation |
| url | https://doi.org/10.1038/s41467-024-54380-1 |
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