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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., 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.

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European J Organic Chem - 2022 - Greis - Neighboring Group Participation of Benzoyl Protecting Groups in C3%u2010 and.pdf (Publisher version), 870KB
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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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 Creators:
Greis, Kim1, 2, Author           
Kirschbaum, Carla1, 2, Author           
Fittolani, Giulio1, 3, Author
Mucha, Eike2, Author           
Chang, Rayoon1, 2, Author           
Helden, Gert von2, Author           
Meijer, Gerard2, Author           
Delbianco, Martina3, Author
Seeberger, Peter H.1, 3, Author
Pagel, Kevin1, 2, Author           
Affiliations:
1Institute of Chemistry and Biochemistry Freie Universität Berlin, Arnimallee 22, 14195 Berlin, Germany, ou_persistent22              
2Molecular Physics, Fritz Haber Institute, Max Planck Society, ou_634545              
3Max Planck Institute of Colloids and Interfaces, Max Planck Society, Am Mühlenberg 1, 14476 Potsdam, DE, ou_1863284              

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Free keywords: Carbohydrates Fluorine Glycosylation IR Spectroscopy Mass spectrometry
 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: 2022-03-022022-03-242022-04-132022-04-21
 Publication Status: Issued
 Pages: 6
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1002/ejoc.202200255
 Degree: -

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Project name : GlycoSpec - Unravelling Glycochemistry with Ion Mobility Spectrometry and Gas-Phase Spectroscopy
Grant ID : 863934
Funding program : Horizon 2020 (H2020)
Funding organization : European Commission (EC)

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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: 6 Volume / Issue: 2022 (15) Sequence Number: e202200255 Start / End Page: - Identifier: ISSN: 1434-193X
CoNE: https://pure.mpg.de/cone/journals/resource/954926953810