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Remote Participation during Glycosylation Reactions of Galactose Building Blocks: Direct Evidence from Cryogenic Vibrational Spectroscopy

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

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Greis,  Kim
Molecular Physics, Fritz Haber Institute, Max Planck Society;

Moon,  Soo-Yeon
Kerry Gilmore, Biomolekulare Systeme, Max Planck Institute of Colloids and Interfaces, Max Planck Society;
Free Univ Berlin, Inst Chem & Biochem;

Pard,  Alonso
Kerry Gilmore, Biomolekulare Systeme, Max Planck Institute of Colloids and Interfaces, Max Planck Society;
Free Univ Berlin, Inst Chem & Biochem;

/persons/resource/persons241114

Kirschbaum,  Carla
Molecular Physics, Fritz Haber Institute, Max Planck Society;
Free Univ Berlin, Inst Chem & Biochem;

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Thomas,  Daniel
Molecular Physics, Fritz Haber Institute, Max Planck Society;

/persons/resource/persons21859

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;

Gilmore,  Kerry
Kerry Gilmore, Biomolekulare Systeme, Max Planck Institute of Colloids and Interfaces, Max Planck Society;

Seeberger,  Peter H.
Free Univ Berlin, Inst Chem & Biochem;
Peter H. Seeberger, Biomolekulare Systeme, Max Planck Institute of Colloids and Interfaces, Max Planck Society;

/persons/resource/persons32738

Pagel,  Kevin
Molecular Physics, Fritz Haber Institute, Max Planck Society;
Free Univ Berlin, Inst Chem & Biochem;

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anie.201916245.pdf
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Citation

Marianski, M., Mucha, E., Greis, K., Moon, S.-Y., Pard, A., Kirschbaum, C., et al. (2020). Remote Participation during Glycosylation Reactions of Galactose Building Blocks: Direct Evidence from Cryogenic Vibrational Spectroscopy. Angewandte Chemie International Edition, 59(15), 6166-6171. doi:10.1002/anie.201916245.


Cite as: http://hdl.handle.net/21.11116/0000-0005-F60D-8
Abstract
The stereoselective formation of 1,2- cis -glycosidic bonds is challenging. However, 1,2- cis -selectivity can be induced by remote participation of C4 or C6 ester groups. Reactions involving remote participation are believed to proceed via a key ionic intermediate, the glycosyl cation. Although mechanistic pathways were postulated many years ago, the structure of the reaction intermediates remained elusive due to their short-lived nature. Here, we unravel the structure of glycosyl cations involved in remote participation reactions via cryogenic vibrational spectroscopy and first principles theory. Acetyl groups at C4 ensure α-selective galactosylations by forming a covalent bond to the anomeric carbon in dioxolenium-type ions. Unexpectedly, also benzyl ether protecting groups can engage in remote participation and promote the stereoselective formation of 1,2- cis -glycosidic bonds.