1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

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3 Discussion and Results 3.2.2.2 FRIEDEL-CRAFTS Acylation to Form the Keto-Exocycle The generated carboxylic acid in 51 could undergo an electrophilic aromatic substitution on the porphyrin macrocycle in terms of a FRIEDEL-CRAFTS reaction. This necessitated the activation of the carboxylic acid by formation of the corresponding acid chloride. 76 As this transformation might go in hand with a protonation of the inner ring nitrogen atoms, lowering the reactivity in the subsequent electrophilic ring closure process, the basic nitrogen atoms had to be protected in advance. This was realized by transformation of free base system 51 into its corresponding copper(II) 97 or nickel(II) complex 97,98 . These two metals are well suited for this purpose since they can easily be inserted and then exhibit a high enough stability towards the reaction conditions. 40 (Scheme 29) While the application of the acetate method proved efficient for the copper(II) insertion, it gave only unsatisfactory results for nickel(II). So the acetylacetonate approach was chosen providing the corresponding nickel(II) complex in high yield. Both Cu(II)-51 and Ni(II)-51 were used as such after aqueous removal of excessive metal salts. 96 40 HO 2 C N NH HN N 51 ClOC HO2C N Ni(II)-52 a N M N N b Cu(II)-51 Ni(II)-51 Scheme 29. Two step procedure for the activation of carboxylic acid 51. a. Cu(OAc)2·2 H2O, CH2Cl2/MeOH/AcOH, rt, 15 h or Ni(acac)2, toluene, reflux, 1.5 h. b. (COCl)2, CH2Cl2, rt, 1.5 h. For the subsequent conversion into the acid chloride, Cu(II)-51 and Ni(II)-51 were reacted with oxalyl chloride, (COCl)2, at rt. Thionyl chloride, SOCl2, could not be used since that led to N N M N N Cu(II)-52 52
N N M N N SnCl 4 CH 2 Cl 2 O N N N M N N M N N Discussion and Results 3 immediate disruption of the porphyrin system. After evaporation of solvent and reagent under high vacuum, the corresponding acid chlorides were directly used for the annulation process being depicted in Scheme 30. ClOC Cu(II)-52 Ni(II)-52 Scheme 30. FRIEDEL-CRAFTS acylation giving enantiomers arising from atropisomerism. Therefore, acid chlorides Cu(II)-52 and Ni(II)-52 were reacted with tin tetrachloride, SnCl4, as LEWIS-Acid “catalyst”. 76 The color of the reaction mixture thereby immediately changed from reddish to dark green indicating the successful annulation. After aqueous work-up, purification of the targeted systems was achieved by FC over silica using mixtures of CH2Cl2 and hexanes as eluents. In doing so, the nickel(II) complex furnished one product Ni(II)-53 in 52 % yield, while the copper(II) precursor gave rise to two distinct fractions. The major one eluting first could be identified as the copper(II) complex of cycloketo-porphyrin system Cu(II)-53 (65 % yield) and the second minor fraction turned out to be the corresponding free base system 53 (< 10 % yield). These observations well conformed to our assumption, that only one product each will be formed appearing as racemic mixture (Scheme 30) in analogy to the cycloamino- porphyrins previously presented 74 . Furthermore, these outcomes implied that, for synthetic means, copper(II) would be the metal of choice as it delivered higher yields and indicated that a demetallation could be achievable leading to free base systems. Both Cu(II)-53 and Ni(II)-53 were fully characterized, but since the characterization data are closely related to those of other metal complexes, they will be presented altogether in paragraph 3.2.4.1. racemic mixture 53 of Cu(II)-53 / Ni(II)-53 O N 41
Page 1 and 2: Semi-Natural and Synthetic Chiral C
Page 3 and 4: Die vorliegende Arbeit entstand in
Page 5 and 6: Table of Contents 1 Introduction 1
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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 first redu
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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 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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