Organocatalytic enantioselective synthesis of double S-shaped quadruple helicene-like molecules
Abstract Helicene-shaped molecules are compelling chemical structures with unique twisted helical chirality and remarkable properties. Although progress occurs in the catalytic asymmetric synthesis of helicene (-like) molecules, the enantioselective synthesis of multiple helicenes, especially four o...
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| Format: | Article |
| Language: | English |
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Nature Portfolio
2025-01-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-024-55590-3 |
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| author | Shengli Huang Haojun Wen Yige Li Wenling Qin Pengfei Wang Yu Lan Shiqi Jia Hailong Yan |
| author_facet | Shengli Huang Haojun Wen Yige Li Wenling Qin Pengfei Wang Yu Lan Shiqi Jia Hailong Yan |
| author_sort | Shengli Huang |
| collection | DOAJ |
| description | Abstract Helicene-shaped molecules are compelling chemical structures with unique twisted helical chirality and remarkable properties. Although progress occurs in the catalytic asymmetric synthesis of helicene (-like) molecules, the enantioselective synthesis of multiple helicenes, especially four or higher helicity, is still challenging and has yet to be achieved. Herein, we report an organocatalytic [4 + 2] cycloadditions to achieve double S-shaped quadruple helicene-like molecules with high enantioselectivity (up to 96% e.e.). The enantioselective synthesis of (P,P,P,P) and (M,M,M,M) configurational quadruple helical molecules can be achieved by modulating the structure of the catalyst. Density functional theory (DFT) calculations show that the reaction involves the formation of a duplex vinylidene ortho-quinone methide (VQM) intermediate and two successive cycloaddition reactions. Configurational stability studies elucidate the isomerization process between the isomers. In addition, the structural features and optical properties of the quadruple helicene-like molecules were investigated to explore their potential applications. |
| format | Article |
| id | doaj-art-9ae2f53cadb443e2912ebafdb2019b65 |
| institution | Kabale University |
| issn | 2041-1723 |
| language | English |
| publishDate | 2025-01-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj-art-9ae2f53cadb443e2912ebafdb2019b652025-01-12T12:31:30ZengNature PortfolioNature Communications2041-17232025-01-0116111210.1038/s41467-024-55590-3Organocatalytic enantioselective synthesis of double S-shaped quadruple helicene-like moleculesShengli Huang0Haojun Wen1Yige Li2Wenling Qin3Pengfei Wang4Yu Lan5Shiqi Jia6Hailong Yan7Green Catalysis Center, College of Chemistry, Zhengzhou UniversityChongqing Key Laboratory of Natural Product Synthesis and Drug Research, Chemical Biology Research Center, School of Pharmaceutical Sciences, Chongqing UniversityChongqing Key Laboratory of Natural Product Synthesis and Drug Research, Chemical Biology Research Center, School of Pharmaceutical Sciences, Chongqing UniversityChongqing Key Laboratory of Natural Product Synthesis and Drug Research, Chemical Biology Research Center, School of Pharmaceutical Sciences, Chongqing UniversityChongqing Key Laboratory of Natural Product Synthesis and Drug Research, Chemical Biology Research Center, School of Pharmaceutical Sciences, Chongqing UniversityGreen Catalysis Center, College of Chemistry, Zhengzhou UniversityGreen Catalysis Center, College of Chemistry, Zhengzhou UniversityChongqing Key Laboratory of Natural Product Synthesis and Drug Research, Chemical Biology Research Center, School of Pharmaceutical Sciences, Chongqing UniversityAbstract Helicene-shaped molecules are compelling chemical structures with unique twisted helical chirality and remarkable properties. Although progress occurs in the catalytic asymmetric synthesis of helicene (-like) molecules, the enantioselective synthesis of multiple helicenes, especially four or higher helicity, is still challenging and has yet to be achieved. Herein, we report an organocatalytic [4 + 2] cycloadditions to achieve double S-shaped quadruple helicene-like molecules with high enantioselectivity (up to 96% e.e.). The enantioselective synthesis of (P,P,P,P) and (M,M,M,M) configurational quadruple helical molecules can be achieved by modulating the structure of the catalyst. Density functional theory (DFT) calculations show that the reaction involves the formation of a duplex vinylidene ortho-quinone methide (VQM) intermediate and two successive cycloaddition reactions. Configurational stability studies elucidate the isomerization process between the isomers. In addition, the structural features and optical properties of the quadruple helicene-like molecules were investigated to explore their potential applications.https://doi.org/10.1038/s41467-024-55590-3 |
| spellingShingle | Shengli Huang Haojun Wen Yige Li Wenling Qin Pengfei Wang Yu Lan Shiqi Jia Hailong Yan Organocatalytic enantioselective synthesis of double S-shaped quadruple helicene-like molecules Nature Communications |
| title | Organocatalytic enantioselective synthesis of double S-shaped quadruple helicene-like molecules |
| title_full | Organocatalytic enantioselective synthesis of double S-shaped quadruple helicene-like molecules |
| title_fullStr | Organocatalytic enantioselective synthesis of double S-shaped quadruple helicene-like molecules |
| title_full_unstemmed | Organocatalytic enantioselective synthesis of double S-shaped quadruple helicene-like molecules |
| title_short | Organocatalytic enantioselective synthesis of double S-shaped quadruple helicene-like molecules |
| title_sort | organocatalytic enantioselective synthesis of double s shaped quadruple helicene like molecules |
| url | https://doi.org/10.1038/s41467-024-55590-3 |
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