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RESEARCH PRODUCT

Inter- and Intramolecular Anodic Nucleophilic Substitutions of Porphyrins. Reactivity of the resulting products

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This manuscript presents the functionalization of porphyrins by anodic nucleophilic substitution (SNAn). After an introduction describing generalities on porphyrin, the 2nd chapter deals with the 2-step synthesis of primary aminoporphyrins. The 1st electrochemical step consists in oxidizing the porphyrin at the 1st oxidation potential in the presence of pyridine. The formed pyridinium-porphyrin is then transformed into an amine by opening the pyridinium fragment by nucleophilic attack of piperidine.The 3rd chapter presents the synthesis and redox reactivity of porphyrins substituted with one (or several) aromatic groups carrying an imine function (thiopyrimidine, quinoline and aminopyridine). Oxidation of these porphyrins leads to the formation of new intramolecular C-N bond(s) leading to cationic planar molecules. In the case of fused thiopyrimidinylporphyrins, new π-extended aminoporphyrins have been prepared by opening the intermediate pyrimidinium ring.The SNAn of free base and magnesium(II), zinc(II) and nickel(II) bisferrocenylporphyrins with triphenylposphosphine was performed by oxidation of the two ferrocene units. A difference in reactivity modulated by the nature of the metal inserted into the cavity of the porphyrin was noted.