Carbohydrates as chiral starting compounds in synthetic organic
chemistry
Lastdrager, Bas
Citation
Lastdrager, B. (2006, March 1). Carbohydrates as chiral starting compounds in synthetic
organic chemistry. Retrieved from https://hdl.handle.net/1887/4368
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/1887/4368
Carbohydrates as
Chi
ral
Starti
ng Compounds
i
n Syntheti
c Organi
c Chemi
stry
PROEFSCHRIFT
ter verkrijging van
de graad van Doctor aan de Universiteit van Leiden, op gezag van Rector M agnificus Dr. D. D. Breimer,
hoogleraar in de faculteit der W iskunde en Natuurwetenschappen en die der Geneeskunde, volgens besluit van het College voor Promoties
te verdedigen op woensdag 1 maart 2006 klokke 15.15 uur
door
Promotiecommissie
Promotor : Prof. dr. H. S. Overkleeft
Co-promotor : Dr. M. Overhand
Referent : Dr. M. A. Leeuwenburgh
Overige leden : Prof. dr. J. Brouwer Dr. G. Lodder
Table of Contents
List of Abbreviations 6
Chapter 1 9
GeneralIntroduction
Chapter 2 39
Towards the Synthesis of trans-Fused Tricyclic Ethers Containing an Angular M ethylGroup:A Selenocyclisation Based Approach
Chapter 3 65
RadicalCyclisation M ediated Synthesis of Conformationally Constrained Ȗ-Sugar Amino Acids
Chapter 4 85
Table of Contents
Chapter 5 111
Claisen Self-Condensation/Decarboxylation as the Key Steps in the Synthesis of C2-Symmetrical 1,7-Dioxaspiro[5.5]undecanes
Chapter 6 127
Summary and Future Prospects
Samenvatting 135
List of Publications 139
Curriculum Vitae 141
6
List of Abbreviations
Ac acetyl
AIBN 2,2’-azobisisobutyronitrile
aq. aqueous
arom. aromatic
b broad
BAIB [bis-(acteoxy)-iodo] benzene
Bn benzyl
Boc tert-butyloxycarbonyl Boc-ON 2-(tert-butoxycarbonyl
oxy-imino)-2-phenylacetonitrile BOP benzotriazol-1-yloxytri
s-(dimethylamino)-phospho nium hexafluorophosphate
Bu butyl
Bz benzoyl
c concentration calcd calculated
CAN ceric (IV) ammonium nitrate cat. catalytic
CSA camphorsulfonic acid CSAA(s) carbasugar amino acid(s) COSY correlated spectroscopy Cq quaternary carbon atom CTX ciguatoxin
Cy cyclohexyl
d doublet
DBU 1,8-diazabicyclo[5.4. 0]undec-7-ene
DCE dichloroethane DCM dichloromethane dd double doublet
ddd double doubletof doublets DEM S diethylmethylsilane DIC diisopropylcarbodiimide DiPEA diisopropylethylamine DM AP 4-(dimethylamino)pyridine DM DP 2,5-dihydroxymethyl-3,
4-dihydroxypyrrolidine DM F dimethylformamide DM S dimethylsulfide DM SO dimethylsulfoxide dppa diphenylphosphorylazide equiv. equivalent
ESI electrospray ionisation
Et ethyl
Fmoc 9-fluorenylmethyloxycarbonyl Glu L-glutamic acid
Gly glycine
List of Abbreviations
7
HCTU 2-(6-chloro-1H-benzotriazol-1-yl)-1,1,3,3-tetramethyl uronium hexafluorophosphate HPLC high performance liquid
chromatography
HPTLC high performance thin layer chromatography
HRMS high resolution mass spectrometry
i iso
IDCP iodonium dicollidine perchlorate
IR infrared
isoprop. isopropylidene J coupling constant
LCMS liquid chromatography mass spectrometry
LDA lithium diisopropylamide Leu L-leucine
LHMDS lithium hexamethyldisilazane
m multiplet
M molecular mass
M molarity
m/z mass to charge ratio
Me methyl
Ms methanesulfonyl MS mass spectrometry
n normal
NMM N-methylmorpholine NMR nuclear magnetic resonance NOE nuclear Overhauser effect NOESY nuclear Overhauser
enhancement spectroscopy NPSP N-(phenylseleno)phthalimide p para P protective group PCC pyridinium chlorochromate PE petroleum ether (40-60) Ph phenyl Phe L-phenylalanine Phth phthaloyl PMB p-methoxybenzyl PMP p-methoxyphenyl ppm part per million
Pr propyl PyBOP benzotriazol-1-yl-oxy-tris-pyrrolidino-phosphonium hexafluorophosphate pyr. pyridine q quartet quant. quantitative RCM ring-closing metathesis rt room temperature Rt retention time SAA(s) sugar amino acid(s) sat. saturated
Su succinimide
t tertiary
t triplet
TBAF tetrabutylammonium fluoride TBAI tetrabutylammonium iodide TBS tert-butyldimethylsilyl TEA triethylamine
TEMPO 2,2,6,6-tetramethyl-1-piperi-dinyloxy free radical
tert tertiary
Tf trifluoromethanesulfonyl TFA trifluoroacetic acid THF tetrahydrofuran TIS triisopropylsilane
