Synthesis of 3,4-diarylpyrroles and conversion into dodecaarylporphyrins; a new approach to porphyrins with altered redox potentials

Abstract

3,4-Diarylpyrroles (1) have been directly prepared in 20–50% yield by the reaction of β-nitrostyrenes with aqueous TiCl₃ in 1,4-dioxane. Pyrroles 1 were also prepared via Barton–Zard pyrrole synthesis using the reaction of α-nitrostilbenes with ethyl isocyanoacetate followed by de-ethoxycarbonylation. 3,4-Diarylpyrroles have been converted into dodecaarylporphyrins by reaction with aromatic aldehydes. Various aryl groups are readily introduced at the periphery of porphyrins by this method. Phenyl substitution at any of the positions of pyrroles decreases E^ox_1/2, while E_1/2^red is almost unchanged. On the other hand, substitution of the 2-thienyl group affects both the HOMO and LUMO energies, and the UV-vis spectra of dodeca-2-thienylporphyrins (4f or 4i) are extremely red-shifted.