Synthesis, spectroscopy, and reactivity of meso-unsubstituted azuliporphyrins and their heteroanalogues. Oxidative ring contractions to carba-, oxacarba-, thiacarba-, and selenacarbaporphyrins.

This paper reports the first detailed study on meso-unsubstituted azuliporphyrins, an important family of porphyrin-like molecules where one of the usual pyrrole rings has been replaced by an azulene subunit. Although the azulene moiety introduces an element of cross-conjugation, zwitterionic resonance contributors with tropylium and carbaporphyrin substructures give azuliporphyrins diatropic character that falls midway between true carbaporphyrins and nonaromatic benziporphyrins. Protonation affords an aromatic dication where this type of resonance interaction is favored due to the associated charge delocalization. Two different "3 + 1" syntheses of meso-unsubstituted azuliporphyrins have been developed. Acid-catalyzed reaction of readily available tripyrrane dicarboxylic acids with 1,3-azulenedicarbaldehyde, followed by oxidation with DDQ or FeCl(3), affords good yields of azuliporphyrins. Alternatively, azulene reacted with acetoxymethylpyrroles (2 equiv) in refluxing acetic acid/2-propanol to give tripyrrane analogues, and following a deprotection step, condensation with a pyrrole dialdehyde in TFA-CH(2)Cl(2) gave the azuliporphyrin system. The latter approach was also used to prepare 23-thia- and 23-selenaazuliporphyrins. However, reaction of the azulitripyrrane with 2,5-furandicarbaldehyde produced a mixture of three oxacarbaporphyrins in moderate yield. The free base forms of thia- and selenaazuliporphyrins both showed intermediary aromatic character that was considerably enhanced upon protonation. The UV-vis spectra for azuliporphyrins and their heteroanalogues showed four bands between 350 and 500 nm and broad absorptions at higher wavelengths. Addition of TFA gave dications that showed porphyrin-like spectra with Soret bands between 460 and 500 nm. In the presence of pyrrolidine, azuliporphyrins and their heteroanalogues undergo nucleophilic attack on the seven-membered ring to give carbaporphyrin adducts. These systems also undergo oxidative rearrangements under basic conditions with t-BuOOH to give benzocarbaporphyrins. The selenaazuliporphyrin afforded two benzoselenacarbaporphyrins, a previously unknown core-modified carbaporphyrin system. The proton NMR spectra for these compounds showed strong diatropic ring currents with the internal CH resonance upfield above -5 ppm, while the meso-protons resonated downfield near 10 ppm. The UV-vis spectra were also porphyrin-like and gave strong Soret bands at ca. 440 nm.