Multiple Click reactions on porphyrins [Elektronische Ressource] = Mehrfache Click-Reaktionen an Porphyrinen / vorgelegt von Nina Lang

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Multiple “Click” Reactions on Porphyrins Mehrfache „Click” Reaktionen an Porphyrinen Der Naturwissenschaftlichen Fakultät der Friedrich-Alexander-Universität Erlangen-Nürnberg zur Erlangung des Doktorgrades Dr. rer. nat. vorgelegt von Nina Lang aus Bamberg Als Dissertation genehmigt von der Naturwissenschaftlichen Fakultät der Friedrich-Alexander-Universität Erlangen-Nürnberg Tag der mündlichen Prüfung: 04. Juni 2010 Versitzender der Prüfungskommission: Prof. Dr. Eberhard Bänsch Erstberichterstatter: Priv.-Doz. Dr. Norbert Jux Zweitberichterstatter: Prof. Dr. Jürgen Schatz Die vorliegende Arbeit entstand in der Zeit von Mai 2006 bis April 2010 am Institut für Organische Chemie der Friedrich-Alexander-Universität Erlangen-Nürnberg. Mein besonderer Dank gilt hierbei meinem Doktorvater PD Dr. Norbert Jux für die Unterstützung und das Interesse am Fortgang meiner Arbeit. For my family "We all want to believe in impossible things, I suppose, to persuade ourselves that miracles can happen." Paul Auster (The Book of Illusions) TABLE OF CONTENTS 1 “CLICK“ CHEMISTRY - A NEW SYNTHETIC PHILOSOPHY 1 1.1 1,3-DIPOLAR CYCLOADDITION - REACTION AND MECHANISM 2 1.2 CONDITIONS FOR CU(I)-CATALYZED 1,3-DIPOLAR CYCLOADDITION 5 1.3 APPLICATIONS OF THE CU(I)-CATALYZED 1,3-DIPOLAR CYCLOADDITION 8 1.3.1 Bioconjugation ..................
Publié le : vendredi 1 janvier 2010
Lecture(s) : 22
Source : D-NB.INFO/100808641X/34
Nombre de pages : 231
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Multiple “Click” Reactions on Porphyrins

Mehrfache „Click” Reaktionen an Porphyrinen
Der Naturwissenschaftlichen Fakultät
der Friedrich-Alexander-Universität Erlangen-Nürnberg zur
Erlangung des Doktorgrades Dr. rer. nat.

vorgelegt von Nina Lang
aus Bamberg















Als Dissertation genehmigt von der Naturwissenschaftlichen Fakultät der Friedrich-
Alexander-Universität Erlangen-Nürnberg


















Tag der mündlichen Prüfung: 04. Juni 2010
Versitzender der Prüfungskommission: Prof. Dr. Eberhard Bänsch
Erstberichterstatter: Priv.-Doz. Dr. Norbert Jux
Zweitberichterstatter: Prof. Dr. Jürgen Schatz


Die vorliegende Arbeit entstand in der Zeit von Mai 2006 bis April 2010 am Institut für
Organische Chemie der Friedrich-Alexander-Universität Erlangen-Nürnberg. Mein
besonderer Dank gilt hierbei meinem Doktorvater PD Dr. Norbert Jux für die
Unterstützung und das Interesse am Fortgang meiner Arbeit.


For my family












"We all want to believe in impossible things,
I suppose, to persuade ourselves that miracles can happen."

Paul Auster (The Book of Illusions)





TABLE OF CONTENTS

1 “CLICK“ CHEMISTRY - A NEW SYNTHETIC PHILOSOPHY 1
1.1 1,3-DIPOLAR CYCLOADDITION - REACTION AND MECHANISM 2
1.2 CONDITIONS FOR CU(I)-CATALYZED 1,3-DIPOLAR CYCLOADDITION 5
1.3 APPLICATIONS OF THE CU(I)-CATALYZED 1,3-DIPOLAR CYCLOADDITION 8
1.3.1 Bioconjugation ........................................................................................................................................................... 8
1.3.2 Material science ....................... 11
1.3.3 Drug Design ............................. 15
1.4 “CLICK” CHEMISTRY ON PORPHYRINS 17
2 PROPOSAL 23
3 RESULTS AND DISCUSSION 25
3.1 FUNDAMENTAL PORPHYRIN BUILDING BLOCKS 25
3.2 FIRST STEPS IN APPLYING THE 1,3-DIPOLAR “CLICK” CYCLOADDITION 31
3.3 SYNTHESIS OF FERROCENE-PORPHYRIN CONJUGATES 41
3.4 SYNTHESIS OF DENDRITIC FERROCENE-PORPHYRIN CONJUGATES 51
3.5 WATER-SOLUBLE FERROCENE-PORPHYRIN SYSTEMS 60
3.5.1 Highly-Substituted Conjugates ................................................................................................................................. 60
3.5.2 Bis-Substituted Water-Soluble Ferrocene-Porphyrin Conjugates .............. 61
3.6 METALATION OF THE FERROCENE-PORPHYRIN CONJUGATES WITH NICKEL, COPPER, MANGANESE AND IRON 65
3.7 THE “CLICK” ROUTE TO “CAPPED” PORPHYRINS 75
3.7.1 Ferrocene-Bridged Porphyrins ................................................................................................................................. 75
3.7.2 Porphyrins Bridged with Dendritic Systems .............. 83
3.7.3 Cyclic Voltammetry of the Bridged Porphyrins .......... 86
3.8 CREATING OLIGOMERIC FERROCENE-PORPHYRIN CONJUGATES 89
3.8.1 Di- and Trimeric Ferrocene-Porphyrin Conjugates .................................................................................................... 89
3.8.2 Synthesis of a Porphyrin-Triad formed of a new AB C-Porphyrin ............. 93 2
3.9 SYNTHESIS OF A NOVEL A B -PORPHYRIN-SYSTEM AND ITS FUNCTIONALIZATION BY “CLICK” CHEMISTRY 100 2 2
3.9.1 Dendritic Functionalization of Bispropargyl Porphyrin 112 ...................................................................................... 102
3.9.2 Ferrocene Conjugates Generated from the Novel A B -Porphyrin .......... 104 2 2
3.10 DIMERS, TRIMERS AND TETRAMERS EXCLUSIVELY CONSTITUTED OF PORPHYRINS 106
3.10.1 Synthesis of Two Different Acetylene Porphyrins ................................................................................................... 106
3.10.2 Combining Acetylene and Azidoporphyrins to Oligomers ....................... 108
3.11 SIDE-SELECTIVE MODIFICATION OF PORPHYRINS 114
4 CONCLUSION AND HIGHLIGHTS 120
5 ZUSAMMENFASSUNG 123
6 EXPERIMENTAL SECTION 126
6.1 CHEMICALS, METHODS AND EQUIPMENT 126
6.2 SYNTHETIC PROCEDURES 129
7 REFERENCES 211








Abbreviations
AChE acetylcholinesterase
AFM atomic force microscopy
Ar aryl
ATR attenuated total reflection
ATRP atom transfer radical polymerization
β-H β-pyrrolic protons (labeling in the depicted NMR spectra)
Boc t-butoxycarbonyl
bpy bispyridin
Bu butyl
COSY correlation spectroscopy
CV cyclic voltammetry
d day(s)
d doublet
DCC dicylcohexylcarbodiimid
trans-2-(3-(4-t-butylphenyl)-
DCTB
2-methyl-2-propenylidene)malononitrile
dd doublet of a doublet
DDQ 2,3-dichloro-5,6-dicyano-1,4-benzoquinone
DHB 2,5-dihydroxybenzoic acid
DIPEA diisopropylethylamine (Hünig‟s base)
DMAP N,N-dimethyl-4-aminopyridine
DMF dimethylformamide
E (E ) (half-wave) potential ½
EA elemental analysis
E , E anodic (cathodic) peak potential pa pc
eq equivalent(s)
et al. et alia
exc. excess(ive)
FAB fast atom bombardment
Fc ferrocene
Fc* decamethylferrocene
Fmoc fluorenylmethoxycarbonyl
GP general procedure
h hour(s)
HETCOR heteronuclear correlation
HIV human immunodeficiency virus
IR Infra-red
m multiplet



M molar
MALDI-TOF matrix assisted laser desorption ionization - time of flight
Me methyl
MS mass spectrometry
NBA nitrobenzyl alcohol
n-BuLi n-butyl lithium
st
NH [G ] NEWKOME dendron 1 generation 2 1
ndNH [G ] NEWKOME dendron 2 generation 2 2
nJ j-coupling (constant) with n indicating
the number of involved bonds
NMR nuclear magnetic resonance
NMRP nitroxide-mediated radical polymerization
Ox oxidation
PBS phosphate buffered saline
PM3 parameterized method No. 3
ppm parts per million
R substituent
RAFT reversible addition fragmentation chain transfer
Red reduction
ROMP ring-opening metathesis polymerization
rt room temperature
s singlet
SAM self-assembled monolayer
SCE standard calomel electrode
sin sinapic acid
SWNTs single-walled carbo nanotubes
t triplet
t tertiary
TBDPS t-butyldiphenylsilyl
TBTA tris(benzyltriazolylmethyl)amine
TCEP tris(2-chlorethyl)phosphate
TEM transmission electron microscopy
TFA trifluoro acetic acid
THF tetrahydrofuran
TLC thin layer chromatography
TPP tetraphenylporphyrin
UV ultraviolet
vis visual
λ wavelength







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