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  Neighboring group participation of benzoyl protecting groups in C3- and C6-fluorinated glucose

Greis, K., Kirschbaum, C., Fittolani, G., Mucha, E., Chang, R., von Helden, G., et al. (2022). Neighboring group participation of benzoyl protecting groups in C3- and C6-fluorinated glucose. European Journal of Organic Chemistry, 2022(15): e202200255. doi:10.1002/ejoc.202200255.

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 Creators:
Greis, Kim, Author
Kirschbaum, Carla, Author
Fittolani, Giulio1, Author              
Mucha, Eike, Author
Chang, Rayoon, Author
von Helden, Gert, Author
Meijer, Gerard, Author
Delbianco, Martina1, Author              
Seeberger, Peter H.2, Author              
Pagel, Kevin, Author
Affiliations:
1Martina Delbianco, Biomolekulare Systeme, Max Planck Institute of Colloids and Interfaces, Max Planck Society, ou_2559692              
2Peter H. Seeberger - Automated Systems, Biomolekulare Systeme, Max Planck Institute of Colloids and Interfaces, Max Planck Society, ou_1863306              

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Free keywords: IR spectroscopy; mass spectrometry; glycosylation; glycosyl cation; fluorine
 Abstract: Fluorination is a potent method to modulate chemical properties of glycans. Here, we study how C3- and C6-fluorination of glucosyl building blocks influence the structure of the intermediate of the glycosylation reaction, the glycosyl cation. Using a combination of gas-phase infrared spectroscopy and first-principles theory, glycosyl cations generated from fluorinated and non-fluorinated monosaccharides are structurally characterized. The results indicate that neighboring group participation of the C2-benzoyl protecting group is the dominant structural motif for all building blocks, correlating with the β-selectivity observed in glycosylation reactions. The infrared signatures indicate that participation of the benzoyl group in enhanced by resonance effects. Participation of remote acyl groups such as Fmoc or benzyl on the other hand is unfavored. The introduction of the less bulky fluorine leads to a change in the conformation of the ring pucker, whereas the structure of the active dioxolenium site remains unchanged.

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Language(s): eng - English
 Dates: 2022-03-242022
 Publication Status: Published in print
 Pages: -
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 Table of Contents: -
 Rev. Type: -
 Identifiers: DOI: 10.1002/ejoc.202200255
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Title: European Journal of Organic Chemistry
  Other : Eur. J. Org. Chem.
Source Genre: Journal
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Publ. Info: Weinheim, Germany : Wiley-VCH
Pages: - Volume / Issue: 2022 (15) Sequence Number: e202200255 Start / End Page: - Identifier: ISSN: 1434-193X