Synthesis of biladienone and bilatrienone by coupled oxidation of tetraarylporphyrins

Tetraarylbiladien-ab-ones bearing various substituents (R) in the para position of the phenyl groups were preprared by coupled oxidation of tetraarylporphyrin iron complexes. The yields of 5,10,15-triaryl-19-aroyl-15-hydroxybiladien-ab-ones were 74% (R = H), 85% (R = OMe), 44% (R = COOMe), and 28% (R = CN). Kinetic studies of the iron porphyrin oxidation revealed that the reaction is accelerated by an electron-withdrawing substituent with the Hammett reaction constant rho = 0.295. 5,10,15-Triaryl-19-aroyl-15-hydroxybiladien-ab-ones undergo the acid-catalyzed elimination reaction either by acetic acid or by mesoporous silica to afford 5,10,15-triaryl-19-aroylbilatrien-abc-one. The elimination reaction in acetic acid is accelerated by an electron-donating substituent with the Hammett reaction constant rho = -1.48.