Examples of internally alkylated azuliporphyrins were prepared by MacDonald-type “3 + 1” condensations. 2-Methyl- and 2-ethylazulene reacted with an acetoxymethylpyrrole in the presence of an acid catalyst to give azulitripyrranes. Following cleavage of the terminal protective groups, condensation with a diformylpyrrole in the presence of hydrochloric acid and oxidation with ferric chloride afforded 21-alkylazuliporphyrins. An azulene dialdehyde similarly reacted with an [Formula: see text]-methyltripyrrane to generate a 23-methylazuliporphyrin. The products could only be isolated in protonated form and the free-base internally alkylated azuliporphyrins proved to be unstable. Nevertheless, the dications are highly diatropic and the internal alkyl group resonances were shifted upfield to beyond -3 ppm. Reaction of a 23-methylazuliporphyrin with palladium(II) acetate primarily afforded a palladium(II) complex with loss of the internal methyl substituent. However, two palladium(II) benzocarbaporphyrins were also identified that were formed by sequential oxidative ring contraction and methyl group migration. Internally alkylated azuliporphyrins provide new insights into the reactivity of the system and the results show that the introduction of alkyl substituents within porphyrinoid cavities greatly modifies the properties of these structures.
An unexpected methyl group migration during on-column Stille derivatization of RNA
