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  Remote participation during glycosylation reactions of galactose building blocks : direct evidence from cryogenic vibrational spectroscopy

Marianski, M., Mucha, E., Greis, K., Moon, S.-Y., Pardo-Vargas, 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. doi:10.1002/anie.201916245.

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Item Permalink: http://hdl.handle.net/21.11116/0000-0005-9BA7-0 Version Permalink: http://hdl.handle.net/21.11116/0000-0006-56AF-5
Genre: Journal Article

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 Creators:
Marianski, Mateusz, Author
Mucha, Eike, Author
Greis, Kim, Author
Moon, Soo-Yeon1, Author              
Pardo-Vargas, Alonso2, Author              
Kirschbaum, Carla, Author
Thomas, Daniel, Author
Meijer, Gerard, Author
von Helden, Gert, Author
Gilmore, Kerry1, Author              
Seeberger, Peter H., Author              
Seeberger, Peter H.2, Author              
Pagel, Kevin, Author
Affiliations:
1Kerry Gilmore, Biomolekulare Systeme, Max Planck Institute of Colloids and Interfaces, Max Planck Society, ou_1863304              
2Peter H. Seeberger - Automated Systems, Biomolekulare Systeme, Max Planck Institute of Colloids and Interfaces, Max Planck Society, ou_1863306              

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Free keywords: IR spectroscopy, Glycans, glycosylation, Glycosyl Cations, Remote Participation
 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.

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Language(s): eng - English
 Dates: 2020-01-16
 Publication Status: Published online
 Pages: -
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 Table of Contents: -
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Title: Angewandte Chemie, International Edition
  Abbreviation : Angew. Chem., Int. Ed.
Source Genre: Journal
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Publ. Info: Weinheim : Wiley-VCH
Pages: - Volume / Issue: - Sequence Number: - Start / End Page: - Identifier: ISSN: 1433-7851