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The Journal of organic chemistry

Preparation of azulene-derived fulvenedialdehydes and their application to the synthesis of stable adj-dicarbaporphyrinoids.


PMID 22288783

Abstract

A "2 + 2" strategy for synthesizing adj-dicarbaporphyrinoid systems has been developed. In a model study, an azulenylmethylpyrrole dialdehyde was condensed with a dipyrrylmethane in the presence of HCl, followed by oxidation with ferric chloride, to give a modest yield of an azuliporphyrin. Fulvene aldehydes were prepared by reacting an indene-derived enamine with azulene aldehydes in the presence of Bu(2)BOTf, and azulene dialdehydes similarly reacted to give fulvene dialdehydes. The dialdehydes were condensed with dipyrrylmethanes in TFA/dichloromethane to afford good to excellent yields of dicarbaporphyrinoids with adjacent indene and azulene subunits. These 22-carbaazuliporphyrins exhibited significant diatropic character, and this property was magnified upon protonation. These characteristics are attributed to tropylium-containing resonance contributors that possess 18π electron delocalization pathways. Protonation studies demonstrated that C-protonation readily occurred at the interior indene carbon, but deuterium exchange also occurred at the internal azulene CH as well as at the meso-positions with TFA-d. Reaction of a carbaazuliporphyrin with silver(I) acetate in methanol or ethanol solutions also gave unusual nonaromatic dialkoxy derivatives.

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