Construction of coumarin-fused pyrido[2,3-b]porphyrins through a trichloroacetic acid-accelerated domino approach

Abstract

The first synthesis to construct coumarin-fused pyrido[2,3-b]porphyrins has been accomplished via a cascade reaction of 2-amino-meso-tetraphenylporphyrins, aromatic aldehydes and 4-hydroxycoumarin in o-dichlorobenzene containing a stoichiometric amount of trichloroacetic acid under reflux conditions. The methodology presented herein provides a direct access to a new series of π-extended nickel(II) and copper(II) porphyrin analogues in 58–69% isolated yields under one-pot operation. Furthermore, coumarin-fused copper(II) pyrido[2,3-b]porphyrin underwent demetalation under the influence of concentrated sulfuric acid to produce free-base porphyrin which on zinc metal insertion using zinc acetate in a chloroform–methanol mixture afforded coumarin-fused zinc(II) pyrido[2,3-b]porphyrin in good yield. The structures of the newly prepared coumarin-fused pyrido[2,3-b]porphyrins were established on the basis of spectral data analysis. In comparison with meso-tetraphenylporphyrin precursors, these porphyrinoids demonstrated a significant red-shift in their electronic absorption and emission spectra.