Glycosyl cations in glycosylation reactions

Hansen, T. (2020)

Doctoral Thesis

This thesis describes the use of a combined approach of computational and experimental techniques to gain novel insights to understand the glycosylation reaction and its reactive intermediates. The research in this thesis shows that glycosyl cations can act as reactive intermediates in glycosylation reactions for the introduction of glycosidic linkages. Furthermore, computational and experimental evidence has been provided showing that dioxolenium ions, formed by participation of remote acyl groups, are relevant reactive intermediates and can effectively steer the stereochemical course of glycosylation reactions. Ultimately, the techniques developed and insights gained in these studies were used in the synthesis of a complex mycobacterial glycolipid. The fundamental knowledge presented in this thesis can be further exploited in future synthetic endeavors, delivering more and more complex glycans to fuel glycobiological and glycomedical research.

• Glycosylation reaction
• Glycosyl cation
• Oxocarbenium ions
• Stereoselectivity
• Reactive intermediates
• Conformational preference
• Reactivity
• Density functional calculations

• All authors: Hansen, T.
• Supervisor: Codée, J.D.C.
• Co-supervisor: Marel, G.A. van der
• Committee: Overkleeft, H.S.; Brouwer, J.; Filippov, D.V.; Bickelhaupt, F.M.; Walvoort, M.T.C.; Woerpel, K.A.
• Qualification: Doctor (dr.)
• Awarding Institution: Leiden Institute of Chemistry (LIC), Faculty of Science, Leiden University
• Date: 2020-11-25
• ISBN (print): 9789464162356