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

Marianski, Mateusz; Mucha, Eike; Greis, Kim; Moon, Soo-Yeon; Pard, Alonso; Kirschbaum, Carla; Thomas, Daniel; Meijer, Gerard; Helden, Gert von; Gilmore, Kerry; Seeberger, Peter H.; Pagel, Kevin

doi:10.1002/anie.201916245

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

MPG-Autoren

/persons/resource/persons183295

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

/persons/resource/persons239542

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;

/persons/resource/persons203721

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

/persons/resource/persons21859

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

/persons/resource/persons21614

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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Zitation

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.

Zitierlink: https://hdl.handle.net/21.11116/0000-0005-F60D-8

Zusammenfassung

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.