dc.contributor.author
Marianski, Mateusz
dc.contributor.author
Greis, Kim
dc.contributor.author
Moon, Sooyeon
dc.contributor.author
Pardo, Alonso
dc.contributor.author
Pagel, Kevin
dc.contributor.author
Kirschbaum, Carla
dc.contributor.author
Seeberger, Peter H.
dc.contributor.author
Mucha, Eike
dc.contributor.author
Thomas, Daniel A.
dc.contributor.author
Meijer, Gerard [u.v.m.]
dc.date.accessioned
2020-04-01T13:20:38Z
dc.date.available
2020-04-01T13:20:38Z
dc.identifier.uri
https://refubium.fu-berlin.de/handle/fub188/27051
dc.identifier.uri
http://dx.doi.org/10.17169/refubium-26812
dc.description.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 owing to their short‐lived nature. Herein, 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.
en
dc.format.extent
6 Seiten
dc.rights.uri
https://creativecommons.org/licenses/by/4.0/
dc.subject
glycosyl cations
en
dc.subject
glycosylation
en
dc.subject
mass spectrometry
en
dc.subject
reaction Intermediates
en
dc.subject
spectroscopy
en
dc.subject.ddc
500 Naturwissenschaften und Mathematik::540 Chemie::547 Organische Chemie
dc.title
Remote participation during glycosylation reactions of galactose building blocks: Direct evidence from cryogenic vibrational spectroscopy
dc.type
Wissenschaftlicher Artikel
dcterms.bibliographicCitation.doi
10.1002/anie.201916245
dcterms.bibliographicCitation.journaltitle
Angewandte Chemie
dcterms.bibliographicCitation.number
15
dcterms.bibliographicCitation.pagestart
6166
dcterms.bibliographicCitation.pageend
6171
dcterms.bibliographicCitation.volume
59
dcterms.bibliographicCitation.url
https://doi.org/10.1002/anie.201916245
refubium.affiliation
Biologie, Chemie, Pharmazie
refubium.affiliation.other
Institut für Chemie und Biochemie / Organische Chemie
refubium.funding
DEAL Wiley
refubium.note.author
Die Publikation wurde von der Freien Universität Berlin finanziert.
refubium.resourceType.isindependentpub
no
dcterms.accessRights.openaire
open access
dcterms.isPartOf.issn
0044-8249
dcterms.isPartOf.eissn
1521-3757