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Benzylidene-Directed Glycosylations - Mechanistic Insights from Cryogenic Infrared Spectroscopy

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Meijer,  Gerard       
Molecular Physics, Fritz Haber Institute, Max Planck Society;

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Helden,  Gert von       
Molecular Physics, Fritz Haber Institute, Max Planck Society;

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Citation

Pagel, K., Chang, C.-W., Greis, K., Kirschbaum, C., Leichnitz, S., Meijer, G., et al. (in preparation). Benzylidene-Directed Glycosylations - Mechanistic Insights from Cryogenic Infrared Spectroscopy.


Cite as: https://hdl.handle.net/21.11116/0000-000E-39C6-3
Abstract
The stereoselective formation of 1,2-cis glycosidic linkages is challenging. The currently most widely used strategy for their installation uses 4,6-O-benzylidene protected building blocks. The stereoselectivity of this reaction is thought to be driven by a covalent intermediate, which reacts via an SN2 mechanism. However, the role of cationic SN1-type intermediates in this reaction is unclear. Here, we elucidate the structure of glycosyl cations carrying 4,6-O-benzylidene groups using cryogenic infrared ion spectroscopy and computational methods. The data reveal that the intermediates unexpectedly form anhydro cations, which correlates well with the stereoselective outcome of SN1-type glycosylations. The study highlights how cryogenic infrared spectroscopy can unravel novel intermediates in sugar chemistry and how this structural data can be linked to reactions in solution.