Premium
Synthesis of A 2 B 6 ‐Type [36]Octaphyrins: Copper(II)‐Metalation‐Induced Fragmentation Reactions to Porphyrins and N ‐Fusion Reactions of meso ‐(3‐Thienyl) Substituents
Author(s) -
Mori Hirotaka,
Aratani Naoki,
Osuka Atsuhiro
Publication year - 2012
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.201100919
Subject(s) - metalation , chemistry , copper , medicinal chemistry , aryl , fragmentation (computing) , molecule , fusion , organic chemistry , linguistics , alkyl , philosophy , computer science , operating system
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.