Sulfonium salt activation in oligosaccharide synthesis
Litjens, Remy E.J.N.
Citation
Litjens, R. E. J. N. (2005, May 31). Sulfonium salt activation in oligosaccharide synthesis. Retrieved from https://hdl.handle.net/1887/3735
Version: Corrected Publisher’s Version
License: Licence agreement concerning inclusion of doctoral thesis in theInstitutional Repository of the University of Leiden Downloaded from: https://hdl.handle.net/1887/3735
Sulfonium Salt Activation In
Oligosacchar
ide Synthesis
PROEFSCHRIFT
t
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verkri
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van
de
graad
van
Doct
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aan
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Uni
versi
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Lei
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van
Rect
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Dr.
D.
D.
Brei
mer,
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facul
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W i
skunde
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Nat
uurwet
enschappen
en
di
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der
Geneeskunde,
vol
gens
besl
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van
het
Col
l
ege
voor
Promot
i
es
t
e
verdedi
gen
op
di
nsdag
31
mei
2005
kl
okke
16.
15
uur
door
Samenstelling Promotiecommissie
Promotores : Prof. dr. G. A. van der Marel Prof. dr. H. S. Overkleeft
Referent : Prof. dr. G. -J. Boons (University of Georgia)
Overige leden : Dr. G. Lodder
Prof. dr. P. H. Seeberger (ETH, Zürich) Prof. dr. J. Lugtenburg
Prof. dr. J. Brouwer
“Die organische Chemie kann einen jetzt ganz toll machen. Sie kommt mir wie ein Urwald der Tropenländer vor, voll der merkwürdigsten Dinge. Ein ungeheures Dickicht, ohne Ausgang und Ende, in das man sich nicht hineinwagen mag.”
Friedrich Wöhler an Jakob Berzelius, 28. Januar 1835.
Table of Contents
List of Abbreviations 6
Chapter 1 General Introduction 9
Chapter 2 A Novel Route Towards the Stereoselective Synthesis of 33 2-Azido-2-Deoxy--D-M annosides
Chapter 3 Sulfonium Triflate M ediated Glycosidations of 45 Aryl 2-azido-2-deoxy-1-thio-D-mannosides
Chapter 4 An Expedient Synthesis of the Repeating Unit of the Acidic 59 Polysaccharide of the Bacteriolytic Complex of Lysoamidase
Chapter 5 Synthesis of an -Gal epitope Gal-(1,3)-Gal-(1,4)-GlcNAc -
Lipid Conjugate 77
Chapter 6 Generic Synthesis of Phenylethanoid Oligosaccharide Backbones 93
Summary and Future Prospects 111
Table of Contents
List of Publications 120
Curriculum Vitae 122
6
List of Abbreviations
Ac acetyl
AIBN ,’-azo-isobutyronitrile
All allyl arom. aromatic aq. aqueous
BAIB [bis(acetoxy)iodo]benzene BDA butane-1,2-diacetal Bn benzyl
BOP benzotriazol-1-yloxytris(dimethylamino)-phosphonium hexafluorophosphate
bs broad singlet
BSP 1-benzenesulfinylpiperidine Bu butyl
Bz benzoyl c concentration cat. catalytic
CDA cyclohexane-1,2-diacetal Cp cyclopentadienyl
Cq quarternary carbon atom
CSA camphor (±)-3-sulfonic acid
chemicalshift
d doublet
DBU 1,8-diazabicyclo[5.4.0]undec-7-ene DCE dichloroethane
DCM dichloromethane dd doubletof doublets
DIBAL-H di-iso-butylaluminium hydride DiPEA N,N-diisopropyl-N-ethylamine DM AP 4-dimethylaminopyridine DM D dimethyldioxirane
List of Abbreviations 7 DMSO dimethylsulfoxide DPS diphenylsulfoxide DTBMP 2,6-di-tert-butyl-4-methylpyridine EDA ethylenediamine
equiv. molar equivalents ESI electrospray ionization Et ethyl
Fmoc 9H-fluoren-9-ylmethoxycarbonyl h hour
HCB 2-(hydroxycarbonyl)benzyl HOBt N-hydroxybenzotriazole
HRMS high resolution mass spectrometry Hz Hertz
i iso
IDCP iodonium di-sym-collidine perchlorate IR infrared spectroscopy J coupling constant m multiplet M molar min minute mp melting point MP p-methoxyphenyl Me methyl MPBT S-(4-methoxyphenyl) Benzenethiosulfinate Ms molecular sieves MS mass spectrometry n normal
NGP neighbouring group participation NIS N-iodosuccinimide
List of Abbreviations
8
Rf retardation factor
RRV relative reactivity value rT room temperature s singlet
SMP S-(p-methoxyphenyl) t tertiary
t triplet
TBAF tetra-n-butylammonium fluoride TBDPS tert-butyldiphenylsilyl
TBS tert-butyldimethylsilyl
TEMPO 2,2,6,6-tetramethyl-1-piperidinyloxy, free radical TEP triethyl phosphite
tert tertiary TES triethylsilyl
Tf trifluoromethanesulfonyl THF tetrahydrofuran
TLC thin layer chromatography TMS trimethylsilyl
TSP trimethylsilyl propionate TTBP 2,4,6-tri-tert-butylpyrimidine U unit
UDP uridine diphosphate UV ultra violet
