University of Groningen
Novel Methods towards Rare Sugars Based on Site-Selective Chemistry
Wan, Ieng Chim (Steven)
DOI:
10.33612/diss.150384050
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Publication date: 2021
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Wan, I. C. S. (2021). Novel Methods towards Rare Sugars Based on Site-Selective Chemistry. University of Groningen. https://doi.org/10.33612/diss.150384050
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Novel Methods towards Rare Sugars
Based on Site-Selective Chemistry
The work described in this thesis was executed at the Stratingh Institute for Chemistry, University of Groningen, the Netherlands.
The authors of this thesis wish to thank the Netherlands Organization for Scientific Research for funding.
Cover and bookmark photo credit: pixabay (User yyryyr1030). Cover co-designed with Vincent Busch.
Novel Methods towards Rare Sugars
Based on Site-Selective Chemistry
Proefschrift
ter verkrijging van de graad van doctor aan de Rijksuniversiteit Groningen
op gezag van de
rector magnificus prof. dr. C. Wijmenga en volgens besluit van het College voor Promoties.
De openbare verdediging zal plaatsvinden op
dinsdag 5 januari 2021 om 11:00 uur
door
Ieng Chim Wan
geboren op 25 juni 1991Promotores
Prof. dr. A. J. Minnaard Prof. dr. M. D. Witte
Beoordelingscommissie Prof. dr. T. Noël
Prof. dr. G. A. van der Marel Prof. dr. J. G. Roelfes
出淤泥而不染 --- 宋
·周敦頤
Table of Contents
Chapter 1. From common monosaccharide to rare monosaccharide: the use of
site-selective reactions ... 1
Definition and basic facts of rare monosaccharides ... 2
The biological relevance of rare monosaccharides ... 3
Traditional approaches on the synthesis of rare monosaccharides vs. direct site-selective modifications. ... 5
Outline of this thesis ... 12
References ... 13
Chapter 2. C3-selective C-C bond formation in unprotected monosaccharides using photoredox catalysis ... 15
Introduction ... 16
Result and discussion ... 17
Conclusion ... 21
Experimental section ... 21
References ... 27
Chapter 3. C3-selective C-C bond formation: optimization and mechanistic study ... 29
Introduction ... 30
Result and discussion ... 32
The problem with incomplete conversion and the unexpected consumption of phenyl vinyl sulfone ... 32
Catalyst loading and conversion ... 44
The role of the solvent ... 48
Product isolation and purification ... 50
Conclusion ... 53
Experimental section ... 54
References ... 60
Chapter 4. From D- to L- monosaccharide derivatives via photodecarboxylation-alkylation ... 63
Introduction ... 64
Conclusion ... 71
Experimental section ... 72
References ... 119
Chapter 5. From the synthesis of N-acetyl-L-talosaminuronic acid to the synthesis of N-acetyl-L-gulosamine via double epimerization ... 123
Introduction ... 124
Result and discussion ... 126
The start of the synthesis and the discovery of the unexpected product . 126 Optimization study for the production of guloside ... 130
Intermezzo; deuterium labelling ... 135
A re-investigation on the work up procedure ... 137
Conclusion ... 139
Work ad futurum ... 140
Experimental section ... 141
References ... 143
Chapter 6. On the origin of regioselectivity in palladium-catalyzed oxidation of glucosides ... 145
Introduction ... 146
Result and discussion ... 149
Conclusion ... 154 Experimental section ... 155 Computational details ... 155 Oxidation of carba-glucosides ... 162 References ... 164 Chapter 7. Summary ... 167 References ... 171 Nederlandse Samenvatting ... 173 Acknowledgement ... 179 Curriculum Vitae ... 183
