Functionalization of Porphyrins: Mechanistic Insights, Conformational Studies, and Structural Characterizations

The condensation of 3‐chloromethylbenzoyl chloride with three atropisomers of meso‐5,10,15,20‐tetrakis(2‐aminophenyl)porphyrin (TAPP) is reported, followed by the reaction of the anion of diethyl malonate to prepare various strapped porphyrins. According to two different geometries of the straps, th...

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Bibliographic Details
Published in:European Journal of Organic Chemistry 2006-03, Vol.2006 (5), p.1207-1215
Main Authors: Halime, Zakaria, Balieu, Sébastien, Lachkar, Mohammed, Roisnel, Thierry, Richard, Philippe, Boitrel, Bernard
Format: Article
Language:English
Subjects:
Cation binding
Chemical Sciences
Porphyrins
Pre-organization
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Summary:The condensation of 3‐chloromethylbenzoyl chloride with three atropisomers of meso‐5,10,15,20‐tetrakis(2‐aminophenyl)porphyrin (TAPP) is reported, followed by the reaction of the anion of diethyl malonate to prepare various strapped porphyrins. According to two different geometries of the straps, the resulting preorganization of the hanging ethoxycarbonyl groups is more or less adapted to the coordination of cations such as lanthanides. The conformational study, as well as the X‐ray structures of three strapped porphyrins, demonstrate that among the three atropisomers investigated in this work, only two of them lead to strapped porphyrins in which an ethoxycarbonyl group is directed towards the centre of the porphyrin. Additionally, we were able to explain some peculiar reactivities observed for single‐strapped porphyrins, as the 5–15 strapped geometry is shown to be favoured. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)
ISSN:1434-193X
1099-0690
DOI:10.1002/ejoc.200500685