University of Groningen
Regioselective modification of carbohydrates for their application as building blocks in
synthesis
Zhang, Ji
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Publication date: 2019
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Zhang, J. (2019). Regioselective modification of carbohydrates for their application as building blocks in synthesis. Rijksuniversiteit Groningen.
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Regioselective modification of Carbohydrates
for their Application as Building Blocks in
Synthesis
The work described in this thesis was carried out at the Stratingh Institute
for Chemistry, University of Groningen, The Netherlands.
The author thanks the financial support from the Chinese Scholarship
Council (CSC).
Cover design by Ji Zhang
Printed by Ipskamp Printing B.V., Enschede, The Netherlands
ISBN: 978-94-034-1517-8 (print)
ISBN: 978-94-034-1516-1 (digital)
Regioselective modification of
Carbohydrates for their Application as
Building Blocks in Synthesis
PhD thesis
to obtain the degree of PhD at the
University of Groningen
on the authority of the
Rector Magnificus Prof. E. Sterken
and in accordance with
the decision by the college of Deans.
This thesis will be defended in public on
Tuesday 19 March 2019 at 11:00 hours
by
Ji Zhang
born on 14 June 1988
Supervisors
Prof. A. J. Minnaard
Prof. M.D. Witte
Assessment Committee
Prof. K. Barta
Prof. P.H. Elsinga
Prof. R.J. Pieters
Contents
Chapter 1. Selective modification of the anomeric and the secondary
hydroxyl groups in carbohydrates ... 1
1.1 Introduction ... 2
1.2 Modification of the anomeric position ... 2
1.2.1 One-pot synthesis of glycoconjugates directly from reducing sugars ... 2
1.2.2 One-pot synthesis of uprotected anomeric glycosyl thiols ... 5
1.3 Site selective modification of the other secondary alcohols ... 8
1.3.1 Site-selective acylation of carbohydrates containing 1,2-cis-diols ... 8
1.3.2 Site-selective O-alkylation and arylation of glycosides ... 9
1.3.3 Site-selective deoxygenation of sugars with H2 over heterogeneous catalysts ... 14
1.3.4. Catalytic regioselective oxidation of carbohydrates ... 16
1.4 Modification at C3 via catalytic oxidation ... 24
1.5 Aim and Outline of this thesis ... 26
1.6 References... 27
Chapter 2. Hydrazine in the Ugi tetrazole reaction ... 33
2.1 Introduction ... 34
2.2 Results and discussion ... 35
2.3 Conclusion... 40
2.4 Experimental section... 40
2.5 References... 51
Chapter 3. A Leuckart–Wallach approach to sugar isocyanides and its IMCRs ... 55
3.1 Introduction ... 56
3.2 Results and discussion ... 58
3.4 Experimental Section ... 61
3.5 References... 68
Chapter 4. Regioselective manipulation of GlcNAc provides allosamine, lividosamine, and related compounds ... 71
4.1 Introduction ... 72
4.2 Results and discussion ... 73
4.3 Conclusion... 78
4.4 Experimental Section ... 78
4.5 References... 95
Chapter 5. The synthesis and antibacterial activity of streptozotocin and its analogues. ... 101
5.1 Introduction ... 102
5.2 The diabetogenic action of STZ ... 102
5.3 Modification of streptozotocin at C3 ... 103
5.4 Preparation of streptozotocin and its analogues... 104
5.5 Antibacterial activity test ... 108
5.6 Conclusion... 113
5.7 Experiment section ... 114
5.8 References... 118
Chapter 6. Protecting group-free reductive chlorination of glycosides via trityl hydrazones ... 121
6.1 Introduction ... 122
6.2 Results and discussion ... 125
6.3 Conclusion... 131
6.4 Experimental Section ... 133
6.5 References... 147
Chapter 7. Summary, conclusion and outlook ... 151
7.1 Summary and conclusion ... 152
7.3 References... 158
Nederlandse Samenvatting ... 161 Acknowledgements ... 165
