Alkylation, metalation and ring contraction of tropiporphyrin

Abstract

Tropiporphyrins are an intriguing class of carbaporphyrinoids that incorporate a cycloheptatriene subunit. Previous investigations have shown that this system acts as a trianionic ligand that can form stable silver(III) complexes. In this work, tropiporphyrin was reacted with excess methyl iodide and potassium carbonate in refluxing acetone to give an internally alkylated derivative. The reaction occurred regioselectively to introduce a methyl group onto the 24-position. Reaction with palladium(II) acetate afforded a palladium(II) complex that retained the [Formula: see text]-methyl substituent. In contrast, reaction of [Formula: see text]-unsubstituted tropiporphyrin with palladium(II) acetate gave two palladium(II) benziporphyrins, one of which possessed a formyl substituent. Although these organometallic derivatives were obtained in relatively low yields, the observation of unexpected ring contraction products demonstrates that the reactivity of the tropiporphyrin system deserves to be further investigated.