1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

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1 Introduction Especially interesting are compounds of basic structures 2, 4 or 7 since those are in close relation to naturally occurring compounds like heme (protoporphyrin IX, 12) found in mammalian blood and many cytochromes, the chlorophylls in plants and bacteria and corrin derivatives in cobalamines (e. g. in vitamin B12). Figure 3. Structures of hemoglobin (left) 25 and cytochrome c (center) 26 both containing iron complexes of protoporphyrin IX (Fe-12) and vitamin B12 (right) 27 based on a corrin structure 13. 6 N NH HN N CO 2 H N N H N CO2H 12 13 Scheme 5. Structure of protoporphyrin IX 12 and basic structure of corrin 13. Because of that great importance, it is easily understandable that a lot of research work has been done on porphyrinoids in order to find out how fundamental processes of life are working. For that purpose, the systems or suitable model compounds have to be made accessible either from nature by isolation procedures or by appropriate synthetic pathways. The latter shall be discussed next. N
<strong>1.1</strong>.2 Syntheses N NH HN N N NH HN N Introduction 1 Like previously presented, the variety of porphyrinoid structures and their substitution patterns is inconceivably large, making a universal synthetic approach unimaginable. Applicable synthetic protocols have to be chosen in respect of number and positions of substituents and also by taking into account the symmetry of the targeted system. Concerning porphyrins themselves, in principle two major substitution patterns are told apart: β- and meso-substitution (Scheme 6). 28,29 Since this work focuses on the latter, only appropriate methods will be discussed further on. 14 15 Scheme 6. Examples for β-substitution (2,3,7,8,12,13,17,18-octaethylporphyrin 14, left) and meso-substitution (5,10,15,20-tetraphenylporphyrin, TPP, 15, right). Historically, the first synthetic approach to meso-substituted porphyrins was accomplished by ROTHEMUND in the 1930’s. He mixed benzaldehyde and pyrrole in a sealed tube and applied high temperature and pressure. These harsh reaction conditions have limited the adaptability towards aldehydes with functional groups tolerating these conditions and furthermore have only given poor yields. 29,30 With the development of chemistry itself, novel catalysts and oxidants became available and allowed further optimization. The works of ADLER & LONGO 29,31 and of LINDSEY 29,32 have represented important milestone therein. Nevertheless, the principle of the reaction remained the same. It is based on condensation and iterative electrophilic substitution steps on the aromatic system of pyrrole (or derivatives) leading to the formation of porphyrinogen 18 via carbinols 16 and carbocation intermediates 17. Tetrapyrrolic macrocycle 18 is finally oxidized to furnish the targeted porphyrin (here TPP, 15). The process is depicted in Scheme 7. 29 For the porphyrinogen formation several catalysts can be applied, amongst others TFA, as a protic catalyst, or LEWIS acids like BF3·OEt2. 33 For the subsequent oxidation, oxygen or substituted quinones like p- chloranil or 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) can be used. 29,32d,34 7
Page 1 and 2: Semi-Natural and Synthetic Chiral C
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3 Discussion and Results utilizatio
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3 Discussion and Results has been d
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3 Discussion and Results other TPP
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3 Discussion and Results Table 10.
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3 Discussion and Results voltammogr
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3 Discussion and Results 3.2.5 Inhe
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3 Discussion and Results effects 12
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3 Discussion and Results 74 Δθ [m
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3 Discussion and Results 3.2.6.2 10
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3 Discussion and Results vibration
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3 Discussion and Results 3.2.6.4 Sy
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3 Discussion and Results cyanomethy
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3 Discussion and Results 3.2.6.5 Co
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3 Discussion and Results phenyl sub
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3 Discussion and Results 3.2.6.5.4
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3 Discussion and Results 90 5 μA -
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3 Discussion and Results 3.2.7 Appr
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3 Discussion and Results (75 eq.) w
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3 Discussion and Results 3.2.7.2 Sy
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3 Discussion and Results of rotatio
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3 Discussion and Results Thus, the
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3 Discussion and Results Time-resol
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3 Discussion and Results correspond
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3 Discussion and Results The remain
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3 Discussion and Results 3.2.8.1 Us
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3 Discussion and Results With all t
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3 Discussion and Results The interm
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3 Discussion and Results 116 HO 2 C
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3 Discussion and Results nitro comp
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3 Discussion and Results The effect
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3 Discussion and Results 3.2.8.2.7
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3 Discussion and Results 3.2.9 Pote
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3 Discussion and Results peak at m/
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3 Discussion and Results Table 25.
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3 Discussion and Results 130
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4 Summary As the characterization d
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5 Zusammenfassung 5 Zusammenfassung
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5 Zusammenfassung Da in guten Ausbe
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6 Experimental Section UV/Vis spect
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6 Experimental Section 6.2 Studied
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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 EA: C57H56N4
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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 6.2.5.9 αα
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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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