title: Synthesis of A2B6-type [36]octaphyrins: copper(II)-metalation-induced fragmentation reactions to porphyrins and N-fusion reactions of meso-(3-thienyl) substituents.
abstract: 5,10,15-Tris(pentafluorophenyl)tetrapyrromethane was efficiently prepared through a route involving stepwise diaroylation of 5-pentafluorophenyldipyrromethane. A(2)B(6)-type [36]octaphyrins were prepared by the cross condensation of the tetrapyrromethane with aryl aldehydes in moderate yields. A(2)B(6)-type [36]octaphyrins bearing 2,4,6-trifluorophenyl, 2,6-dichlorophenyl, and phenyl substituents underwent Cu(II)-metalation-induced fragmentation to give two molecules of AB(3)-type Cu(II) porphyrins. A(2)B(6)-type [36]octaphyrin bearing 3-thienyl substituents underwent thermal N-thienyl fusion reactions to provide a modestly aromatic [38]octaphyrin, which, upon treatment with MnO(2), underwent further N-thienyl fusion and subsequent oxidation to give a nonaromatic doubly N-thienyl fused [36]octaphyrin.
authors.affiliation: Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502, Japan.
authors.forename: Hirotaka
authors.initials: H
authors.lastname: Mori
authors.forename: Naoki
authors.initials: N
authors.lastname: Aratani
authors.forename: Atsuhiro
authors.initials: A
authors.lastname: Osuka