1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

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3 Discussion and Results 3.2.7 Approaching Polyexocyclic Cycloketo-Porphyrin Systems By considering the formation of poly-annulated systems, one has to keep in mind that the formation of a ketone exocycle, like it is present in 53, causes dissymmetry within the system as the closure process might occur from above or below the porphyrin plane. This is of less relevance for mono-functional precursors as then enantiomers are formed (e.g. simplified representable by � and �) having the same chemical and physical properties. By switching to bis-functional precursors, this fact becomes of vital importance as different kinds of ring closure can provide compounds of diastereomeric relation with different chemical and physical characteristics. Additionally, one second aspect concerning regiochemistry has to be included into considerations, as in mono-functionalized precursors both pyrrolic units, the ring closure can occur to, are equivalent. If one annulation has taken place, these units become differentiable providing additional possible products. Thus, from one bis-functional starting compound, in principle four products can be obtained in one reaction; pictorially represented by ��, ��, �� and ��, (see Scheme 46) plus corresponding enantiomers. Evidently, some control in terms of pre-organization has to be exerted to prevent ending up in inseparable mixtures. Fortunately, the already introduced building-blocks (Scheme 17) provide the capability to control at least some regiochemistry since they are accessible as compounds with defined and stable αα- (48) and αβ-conformation (47). 69 Starting from a precursor like 46 represents an even simpler alternative as there both functional groups are situated on the same phenyl ring allowing only one possible ring closure scenario to give enantiomeric structures. The following paragraphs will hence concentrate on bis-functional compounds derived from the abovementioned possible starting materials 46, 47 and 48 whose syntheses have already been presented in paragraph 3.2.1. A pictorial outline showing the relations between them and the corresponding bis-cycloketo-porphyrins is included in Scheme 46. 92
Br Br N NH HN N Br 48 N NH HN N 47 Br Br Br N NH HN N O O N NH HN N N NH HN N Discussion and Results 3 N NH HN N O 69 (�� ) 70 (��) O O N NH HN N O 67 (�� ) 68 (�� ) O O N NH HN N Scheme 46. Possible structures of bis-annulated systems: 67 and 68 arising from 48, 69 and 70 from 47, and 71 from 46, respectively. For 68, 69 and 71 only one representative enantiomer is displayed while 67 and 70 are supposed to be „meso-forms“. 3.2.7.1 Porphyrin Di-Ethanoic Acid Derivatives 46 71 (�� ) As the general procedures to access porphyrin ethanoic acid derivatives have already been optimized for mono-functional compounds, the pathway for the conversions of 46, 47 and 48 to the corresponding porphyrin di-ethanoic acids appeared straightforward. Firstly, bromomethyl porphyrin systems 46-48 were converted into the accordant cyanomethyl derivatives 72-74 by application of the same general conditions 96 via zinc(II) complex intermediates. In contrast to mono-functional derivatives, a higher amount of KCN O O 93
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Semi-Natural and Synthetic Chiral C
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Die vorliegende Arbeit entstand in
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Table of Contents 1 Introduction 1
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n J j-coupling (constant) with n in
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1 Introduction characteristics. For
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1 Introduction 1.1 Porphyrins - A G
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1 Introduction Especially interesti
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1 Introduction 8 [H] 4 + 4 O H O H
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1 Introduction complexes are usuall
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1 Introduction transitions as it is
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1 Introduction 1.2 Photodynamic The
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1 Introduction Certainly, Photofrin
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1 Introduction intact membranes bei
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1 Introduction components, the limi
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2 State of The Art & Aims They were
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2 State of The Art & Aims 2.2 Aim o
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3 Discussion and Results encapsulat
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3 Discussion and Results diastereot
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3 Discussion and Results 30 E ½ Re
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3 Discussion and Results irradiatio
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3 Discussion and Results 34 R 1 O N
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3 Discussion and Results 3.2.2.1.2
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3 Discussion and Results Table 4. S
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3 Discussion and Results 3.2.2.2 FR
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Page 86 and 87: 3 Discussion and Results vibration
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Page 140 and 141: 4 Summary As the characterization d
Page 142 and 143: 5 Zusammenfassung 5 Zusammenfassung
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6 Experimental Section 13 C NMR (10
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6 Experimental Section (cyanomethyl
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6 Experimental Section 6.2.4 AB3-Ty
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6 Experimental Section 6.2.4.3 5 4
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6 Experimental Section 6.2.4.11 10
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6 Experimental Section EA: C57H56N4
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6 Experimental Section 6.2.4.15 10
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6 Experimental Section 6.2.5 A2B2-T
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6 Experimental Section 6.2.5.5 αβ
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6 Experimental Section 6.2.5.7 αβ
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6 Experimental Section 6.2.5.9 αα
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6 Experimental Section 6.2.5.11 α
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6 Experimental Section 6.2.5.13 α
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6 Experimental Section 6.2.6 AB2C-T
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6 Experimental Section UV/Vis (CH2C
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6 Experimental Section UV/Vis (CH2C
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6 Experimental Section broad signal
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7 References 16 H. Fischer, K. Zeil
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7 References 57 S. Schwartz, K. Abs
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7 References 89 (a) R. C. Fuson, J.
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7 References 131 (a) J. Perdew, Phy
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S. Jasinski, N. Jux, “Investigati
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Ein großer Dank gilt auch den Ange
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Cirruculum vitae Stefan Jasinski Ge
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1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

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