Exploiting π and Chalcogen Interactions for the β‐Selective Glycosylation of Indoles through Glycal Conformational Distortion
Abstract: Harnessing unconventional noncovalent interactions (NCIs) is emerging as a formidable synthetic approach in difficult‐to‐access glycosidic chemical space. C‐Glycosylation, in particular, has gained a flurry of recent attention. However, most reported methods are restricted to the relatively facile access to α‐C‐glycosides. Herein, we disclose a β‐stereoselective glycosylation of indoles by employing a phosphonoselenide catalyst. The robustness of this protocol is exemplified by its amenability for reaction at both the indolyl C‐ and N‐ reactivity sites. In contrast to previous reports, in which the chalcogens were solely involved in Lewis acidic activation, our mechanistic investigation unraveled that the often neglected flanking aromatic substituents of phosphonoselenides can substantially contribute to catalysis by engaging in π‐interactions. Computations and NMR spectroscopy indicated that the chalcogenic and aromatic components of the catalyst can be collectively exploited to foster conformational distortion of the glycal away from the usual half‐chair to the boat conformation, which liberates the convex β‐face for nucleophilic attack.
- Location
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Deutsche Nationalbibliothek Frankfurt am Main
- Extent
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Online-Ressource
- Language
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Englisch
- Bibliographic citation
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Exploiting π and Chalcogen Interactions for the β‐Selective Glycosylation of Indoles through Glycal Conformational Distortion ; day:10 ; month:01 ; year:2024 ; extent:15
Angewandte Chemie ; (10.01.2024) (gesamt 15)
- Creator
- DOI
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10.1002/ange.202316667
- URN
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urn:nbn:de:101:1-2024011114215500910279
- Rights
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Open Access; Der Zugriff auf das Objekt ist unbeschränkt möglich.
- Last update
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15.08.2025, 7:30 AM CEST
Data provider
Deutsche Nationalbibliothek. If you have any questions about the object, please contact the data provider.
Associated
- Guo, Hao
- Kirchhoff, Jan‐Lukas
- Strohmann, Carsten
- Grabe, Bastian Martin
- Loh, Charles C. J.
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