Neighboring Group Participation of Benzoyl Protecting Groups in C3- and 
C6-Fluorinated Glucose

Greis, Kim; Kirschbaum, Carla; Fittolani, Giulio; Mucha, Eike; Chang, Rayoon; Helden, Gert von; Meijer, Gerard; Delbianco, Martina; Seeberger, Peter H.; Pagel, Kevin

doi:10.1002/ejoc.202200255

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Neighboring Group Participation of Benzoyl Protecting Groups in C3- and C6-Fluorinated Glucose

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Greis, Kim
Institute of Chemistry and Biochemistry Freie Universität Berlin;
Molecular Physics, Fritz Haber Institute, Max Planck Society;

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Kirschbaum, Carla
Institute of Chemistry and Biochemistry Freie Universität Berlin;
Molecular Physics, Fritz Haber Institute, Max Planck Society;

Fittolani, Giulio
Institute of Chemistry and Biochemistry Freie Universität Berlin;
Max Planck Institute of Colloids and Interfaces, Max Planck Society;

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Mucha, Eike
Molecular Physics, Fritz Haber Institute, Max Planck Society;

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Chang, Rayoon
Institute of Chemistry and Biochemistry Freie Universität Berlin;
Molecular Physics, Fritz Haber Institute, Max Planck Society;

/persons/resource/persons21614

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

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

Delbianco, Martina
Max Planck Institute of Colloids and Interfaces, Max Planck Society;

Seeberger, Peter H.
Institute of Chemistry and Biochemistry Freie Universität Berlin;
Max Planck Institute of Colloids and Interfaces, Max Planck Society;

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Pagel, Kevin
Institute of Chemistry and Biochemistry Freie Universität Berlin;
Molecular Physics, Fritz Haber Institute, Max Planck Society;

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European J Organic Chem - 2022 - Greis - Neighboring Group Participation of Benzoyl Protecting Groups in C3%u2010 and.pdf
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Citation

Greis, K., Kirschbaum, C., Fittolani, G., Mucha, E., Chang, R., Helden, G. v., 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.

Cite as: https://hdl.handle.net/21.11116/0000-000A-533C-6

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.