Synthesis and Characterization of N-Methylporphyrins, Heteroporphyrins, Carbaporphyrins, and Related Systems.

MacDonald-type "3 + 1" condensations of an N-methyltripyrrane with a series of dialdehydes afforded a matched set of N-methylporphyrins, N-methylheteroporphyrins, N-methyloxybenziporphyrin, N-methyloxypyriporphyrin, N-methyltropiporphyrin, and a N-methylcarbaporphyrin aldehyde. meso-Unsubstituted heteroporphyrins have been little explored previously, and this strategy was also used to prepare N-unsubstituted 21-oxa-, 21-thia-, and 21-selenaporphyrins. In every case, the N-methylporphyrinoids exhibited weaker, bathochromically shifted UV-Vis absorptions compared to their core unsubstituted congeners. However, proton NMR spectroscopy demonstrated that these derivatives retained strong diamagnetic ring currents and the presence of the internal alkyl substituents had little effect on the global aromatic characteristics. Nevertheless, the UV-Vis spectra of N-methyl-oxybenzi- and N-methyl-oxypyriporphyrins were dramatically altered and gave greatly weakened absorptions. N-Methyl-oxybenzi- and N-methyltropiporphyrins reacted with palladium(II) acetate to give stable palladium(II) complexes, demonstrating that N-alkylation alters the metalation properties for these carbaporphyrinoids. The organometallic derivatives also retained strongly aromatic properties, and the proton NMR spectra showed the N-methyl resonances near -3 ppm. N-Methylcarbaporphyrin-2-carbaldehyde also gave a palladium(II) complex, but this gradually rearranged at higher temperatures to afford a C-methyl complex. The results demonstrate that core alkylation of porphyrinoids greatly alters the reactivity and spectroscopic properties for these systems.