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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., 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.

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 Creators:
Marianski, Mateusz1, 2, Author
Mucha, Eike3, Author              
Greis, Kim3, Author              
Moon, Soo-Yeon4, 5, Author
Pard, Alonso4, 5, Author
Kirschbaum, Carla3, 5, Author              
Thomas, Daniel3, Author              
Meijer, Gerard3, Author              
Helden, Gert von3, Author              
Gilmore, Kerry4, Author
Seeberger, Peter H.5, 6, Author
Pagel, Kevin3, 5, Author              
Affiliations:
1CUNY Hunter Coll, Dept Chem & Biochem, 695 Pk Ave, New York, NY 10065 USA, ou_persistent22              
2UNY, Grad Ctr, PhD Program Chem, 365 5th Ave, New York, NY 10016 USA, ou_persistent22              
3Molecular Physics, Fritz Haber Institute, Max Planck Society, ou_634545              
4Kerry Gilmore, Biomolekulare Systeme, Max Planck Institute of Colloids and Interfaces, Max Planck Society, ou_1863304              
5Free Univ Berlin, Inst Chem & Biochem, Takustrasse 3, D-14195 Berlin, Germany, ou_persistent22              
6Peter H. Seeberger, Biomolekulare Systeme, Max Planck Institute of Colloids and Interfaces, Max Planck Society, ou_2040285              

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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: 2019-12-182020-01-162020-04-06
 Publication Status: Published in print
 Pages: 6
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1002/anie.201916245
 Degree: -

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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: 6 Volume / Issue: 59 (15) Sequence Number: - Start / End Page: 6166 - 6171 Identifier: ISSN: 1433-7851
CoNE: https://pure.mpg.de/cone/journals/resource/1433-7851