期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 58, 期 39, 页码 13758-13762出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201907001
关键词
conformation analysis; fluorine; glycosylation; reaction mechanisms; superacids
资金
- Agence Nationale de la Recherche (ANRs SweetCat and Oxycarb)
- European Union (ERDF)
- Region Nouvelle Aquitaine
- University of Poitiers
- European Research Council [336376-ChMiFluorS, 788143-RECGLYCANMR]
- Agencia Estatal de Investigacion (Spain) [CTQ2015-64597-C2-1-P]
- Severo Ochoa Excellence Accreditation [SEV-2016-0644]
An expansive NMR-based structural analysis of elusive glycosyl cations derived from natural and non-natural monosaccharides in superacids is disclosed. For the first time, it has been possible to explore the consequence of deoxygenation and halogen substitution at the C2 position in a series of 2-halogenoglucosyl, galactosyl, and mannosyl donors in the condensed phase. These cationic intermediates were characterized using low-temperature in situ NMR experiments supported by DFT calculations. The 2-bromo derivatives display intramolecular stabilization of the glycosyl cations. Introducing a strongly electron-withdrawing fluorine atom at C2 exerts considerable influence on the oxocarbenium ion reactivity. In a superacid, these oxocarbenium ions are quenched by weakly coordinating SbF6- anions, thereby demonstrating their highly electrophilic character and their propensity to interact with poor nucleophiles.
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