Catalyst-free and wavelength-tuned glycosylation based on excited-state intramolecular proton transfer
Abstract The chemoselectivity of organic reactions is a fundamental topic in organic chemistry. In the long history of chemical synthesis, achieving chemoselectivity is mainly limited to thermodynamic conditions by an exogenous activation strategy. Here, we design an endogenous activation method, wh...
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| Format: | Article |
| Language: | English |
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Nature Portfolio
2024-11-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-024-54020-8 |
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| author | Min Hou Xiaoling Jing Guoen Wen Haibing He Shuanhu Gao |
| author_facet | Min Hou Xiaoling Jing Guoen Wen Haibing He Shuanhu Gao |
| author_sort | Min Hou |
| collection | DOAJ |
| description | Abstract The chemoselectivity of organic reactions is a fundamental topic in organic chemistry. In the long history of chemical synthesis, achieving chemoselectivity is mainly limited to thermodynamic conditions by an exogenous activation strategy. Here, we design an endogenous activation method, which can be used to control the chemoselectivity of phenol and naphthol through the photo-induced excited-state intramolecular proton transfer (ESIPT). A wavelength-tuned glycosylation is developed to showcase the penitential of this new strategy. Traditionally, an exogenous activator (electrophilic promoters) is essential to induce the cleave of a polar single bond, and this strategy has been extensively studied and used in the glycosylation chemistry, for the formation of oxocarbenium cation intermediate. In our systems, the oxocarbenium cation intermediates can be selectively formed from glycosyl donors bearing tunable chromophoric groups under mild conditions of acid-base free and redox neutrality, which enables continuous synthesis of oligosaccharides. |
| format | Article |
| id | doaj-art-3601a9f3b4d94e568e07e06fbb20a341 |
| institution | Kabale University |
| issn | 2041-1723 |
| language | English |
| publishDate | 2024-11-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj-art-3601a9f3b4d94e568e07e06fbb20a3412024-11-10T12:33:07ZengNature PortfolioNature Communications2041-17232024-11-011511910.1038/s41467-024-54020-8Catalyst-free and wavelength-tuned glycosylation based on excited-state intramolecular proton transferMin Hou0Xiaoling Jing1Guoen Wen2Haibing He3Shuanhu Gao4Wuhu Hospital Affiliated to East China Normal University, East China Normal UniversityState Key Laboratory of Petroleum Molecular & Process Engineering, Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal UniversityState Key Laboratory of Petroleum Molecular & Process Engineering, Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal UniversityShanghai Frontiers Science Center of Molecule Intelligent Syntheses, School of Chemistry and Molecular Engineering, East China Normal UniversityWuhu Hospital Affiliated to East China Normal University, East China Normal UniversityAbstract The chemoselectivity of organic reactions is a fundamental topic in organic chemistry. In the long history of chemical synthesis, achieving chemoselectivity is mainly limited to thermodynamic conditions by an exogenous activation strategy. Here, we design an endogenous activation method, which can be used to control the chemoselectivity of phenol and naphthol through the photo-induced excited-state intramolecular proton transfer (ESIPT). A wavelength-tuned glycosylation is developed to showcase the penitential of this new strategy. Traditionally, an exogenous activator (electrophilic promoters) is essential to induce the cleave of a polar single bond, and this strategy has been extensively studied and used in the glycosylation chemistry, for the formation of oxocarbenium cation intermediate. In our systems, the oxocarbenium cation intermediates can be selectively formed from glycosyl donors bearing tunable chromophoric groups under mild conditions of acid-base free and redox neutrality, which enables continuous synthesis of oligosaccharides.https://doi.org/10.1038/s41467-024-54020-8 |
| spellingShingle | Min Hou Xiaoling Jing Guoen Wen Haibing He Shuanhu Gao Catalyst-free and wavelength-tuned glycosylation based on excited-state intramolecular proton transfer Nature Communications |
| title | Catalyst-free and wavelength-tuned glycosylation based on excited-state intramolecular proton transfer |
| title_full | Catalyst-free and wavelength-tuned glycosylation based on excited-state intramolecular proton transfer |
| title_fullStr | Catalyst-free and wavelength-tuned glycosylation based on excited-state intramolecular proton transfer |
| title_full_unstemmed | Catalyst-free and wavelength-tuned glycosylation based on excited-state intramolecular proton transfer |
| title_short | Catalyst-free and wavelength-tuned glycosylation based on excited-state intramolecular proton transfer |
| title_sort | catalyst free and wavelength tuned glycosylation based on excited state intramolecular proton transfer |
| url | https://doi.org/10.1038/s41467-024-54020-8 |
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