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  The Influence of the Electron Density in Acyl Protecting Groups on the Selectivity of Galactose Formation

Greis, K., Leichnitz, S., Kirschbaum, C., Chang, C.-W., Lin, M.-H., Meijer, G., et al. (2022). The Influence of the Electron Density in Acyl Protecting Groups on the Selectivity of Galactose Formation. Journal of the American Chemical Society, 144(44), 20258-20266. doi:10.1021/jacs.2c05859.

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 Urheber:
Greis, Kim1, Autor           
Leichnitz, Sabrina, Autor
Kirschbaum, Carla1, Autor           
Chang, Chun-Wei, Autor
Lin, Mei-Huei, Autor
Meijer, Gerard1, Autor           
Helden, Gert von1, Autor           
Seeberger, Peter H., Autor
Pagel, Kevin1, Autor           
Affiliations:
1Molecular Physics, Fritz Haber Institute, Max Planck Society, ou_634545              

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Schlagwörter: Cations; Chemical structure; Free radicals; Post-translational modification; Protective groups
 Zusammenfassung: The stereoselective formation of 1,2-cis-glycosidic bonds is a major bottleneck in the synthesis of carbohydrates. We here investigate how the electron density in acyl protecting groups influences the stereoselectivity by fine-tuning the efficiency of remote participation. Electron-rich C4-pivaloylated galactose building blocks show an unprecedented α-selectivity. The trifluoroacetylated counterpart with electron-withdrawing groups, on the other hand, exhibits a lower selectivity. Cryogenic infrared spectroscopy in helium nanodroplets and density functional theory calculations revealed the existence of dioxolenium-type intermediates for this reaction, which suggests that remote participation of the pivaloyl protecting group is the origin of the high α-selectivity of the pivaloylated building blocks. According to these findings, an α-selective galactose building block for glycosynthesis is developed based on rational considerations and is subsequently employed in automated glycan assembly exhibiting complete stereoselectivity. Based on the obtained selectivities in the glycosylation reactions and the results from infrared spectroscopy and density functional theory, we suggest a mechanism by which these reactions could proceed.

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Sprache(n): eng - English
 Datum: 2022-06-022022-10-272022-11-09
 Publikationsstatus: Erschienen
 Seiten: 9
 Ort, Verlag, Ausgabe: -
 Inhaltsverzeichnis: -
 Art der Begutachtung: Expertenbegutachtung
 Identifikatoren: DOI: 10.1021/jacs.2c05859
 Art des Abschluß: -

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Projektname : GlycoSpec - Unravelling Glycochemistry with Ion Mobility Spectrometry and Gas-Phase Spectroscopy
Grant ID : 863934
Förderprogramm : Horizon 2020 (H2020)
Förderorganisation : European Commission (EC)

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Titel: Journal of the American Chemical Society
  Andere : JACS
  Kurztitel : J. Am. Chem. Soc.
Genre der Quelle: Zeitschrift
 Urheber:
Affiliations:
Ort, Verlag, Ausgabe: Washington, DC : American Chemical Society
Seiten: 9 Band / Heft: 144 (44) Artikelnummer: - Start- / Endseite: 20258 - 20266 Identifikator: ISSN: 0002-7863
CoNE: https://pure.mpg.de/cone/journals/resource/954925376870