Oxacarbenium ion intermediates in the stereoselective synthesis of anionic oligosaccharides
Dinkelaar, J.
Citation
Dinkelaar, J. (2009, May 13). Oxacarbenium ion intermediates in the stereoselective synthesis of anionic oligosaccharides. Retrieved from https://hdl.handle.net/1887/13791
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Oxacarbenium ion intermediates in the stereoselective synthesis of anionic oligosaccharides
PROEFSCHRIFT
ter verkrijging van
de graad van Doctor aan de Universiteit Leiden,
op gezag van de Rector Magnificus prof. Mr. P.F. van der Heijden, volgens besluit van het College voor Promoties
te verdedigen op woensdag 13 mei 2009 klokke 15:00
door
Jasper Dinkelaar
Geboren te Amsterdam in 1979
Promotiecommissie
Promotor : Prof. dr. G.A. van der Marel Co-promotor : Dr. J.D.C. Codée
Overige leden : Prof. dr. G.-J. Boons (University of Georgia) Dr. L.J. van den Bos (Schering-Plough) Prof. dr. J. Brouwer
Prof. dr. H. Hiemstra (Universiteit van Amsterdam) Dr. G. Lodder
Prof. dr. J. Lugtenburg
Dr. J.H. van Maarseveen (Universiteit van Amsterdam) Prof. dr. H.S. Overkleeft
De totstandkoming van dit proefschrift werd mede mogelijk gemaakt met een financiële
bijdrage in de drukkosten door de J.E. Jurriaanse Stichting.
Table of Contents
List of Abreviations 6
Chapter 1 9
General introduction: stereoselectivity of reactive intermediates in glycosylation reactions
Chapter 2 29
NIS/TFA: A General Method for Hydrolyzing Thioglycosides
Chapter 3 39
Synthesis of Hyaluronic Acid Oligomers using Ph
2SO/Tf
2O Mediated Glycosylations
Chapter 4 53
Synthesis of Hyaluronic Acid Oligomers using Chemoselective and
One-Pot Strategies
Chapter 5 75 Stereoselective Synthesis of
L-Guluronic Acid Alginates
Chapter 6 103
Stereodirecting Effect of the Pyranosyl C-5 Substituent in Glycosylation Reactions
Chapter 7 131
Summary and Future Prospects
Samenvatting 137
List of Publications 140
Curriculum Vitea 142
Nawoord 143
List of abbreviations
Ac acetyl HA hyaluronan
ACN acetonitrile HPLC high performance liquid chromatography
All allyl HRMS high resolution mass spectrometry
Arom aromatic Hz Hertz
aq. aqueous IDCP iodonium di-syn-collidine perchlorate BAIB [bis(acetoxy)iodo]benzene IR infrared spectroscopy
Bn benzyl isoprop isopropylidene
bs broad singlet J coupling constant
BSP 1-benzenesulfinyl piperidine LCMS liquid chromatography mass spectrometry
Bu butyl Lev levulinoyl
Bz benzoyl m multiplet
cat. catalytic M molar
ClAc chloroacetyl Me methyl
Cq quarternary carbon atom MS3Å molecular sieves 3 Ångström
d doublet MS mass spectrometry
DBU 1,8-diazabicyclo[5.4.0]undec-7-ene NBS N-bromosuccinimide
DCM dichloromethane NIS N-iodosuccinimide
DNP dinitrophenyl NMR nuclear magnetic resonance
DTBS di-tert-butyl-silylidene p para
dd doublet of doublets P protective group DIBAL-H di-iso-butylaluminium hydride PE petroleum ether DiPEA N,N-di-iso-propyl-N-ethylamine Pent pentenyl DMAP 4-dimethylaminopyridine Ph phenyl
DMF N,N-dimethylformamide Phth phthaloyl
DMSO dimethylsulfoxide pMB p-methoxybenzyl dq doublet of quartets pMP p-methoxyphenyl dt doublet of triplets ppm parts per million DTBMP 2,6-di-tert-butyl-4-methylpyridine Pr propyl equiv. molar equivalents pyr. pyridine ESI electrospray ionization q quartet
Et ethyl rT room temperature
s singlet tert tertiary
sat. saturated Tf trifluoromethanesulfonyl
tBu tert-butyl TFA trifluoroacetic acid
t triplet THF tetrahydrofuran
TBABr tetra-n-butylammonium bromide TLC thin layer chromatography TBAI tetra-n-butylammonium iodide Tol p-toluyl
TBDPS tert-butyldiphenylsilyl TMS trimethylsilyl
TBDMS tert-butyldimethylsilyl Tr trityl / triphenylmethyl TBS tert-butyldimethylsilyl Ts tosyl / p-toluenesulfonyl TCA trichloroacetyl TTBP 2,4,6-tri-tert-butylpyrimidine TLR Toll like receptor UV ultraviolet
TEMPO 2,2,6,6-tetramethyl-1-piperidinyloxy
