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% (...

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Published inJournal of organic chemistry Vol. 72; no. 14; pp. 5320 - 5326
Main Authors Asano, Naomi, Uemura, Sayo, Kinugawa, Tomoya, Akasaka, Hiroaki, Mizutani, Tadashi
Format Journal Article
LanguageEnglish
Published WASHINGTON American Chemical Society 06.07.2007
Amer Chemical Soc
Subjects
Chemistry
Chemistry, Organic
Exact sciences and technology
Heterocyclic compounds
Heterocyclic compounds with several n hetero atoms in the same ring, in separated rings or in fused rings
Kinetics and mechanisms
Organic chemistry
Physical Sciences
Preparations and properties
Reactivity and mechanisms
Science & Technology
HEME OXYGENASE
ZINC BILINDIONES
REACTION REGIOSPECIFICITY
PROTOPORPHYRIN-IX
ELECTRONIC CONTROL
MESO-TETRAPHENYLPORPHYRIN
VERDOHEME ANALOGS
CHEMICAL OXIDATION
PHOTO-OXYGENATION
AMINO-ACID ESTERS
Iron Complexes
Transition metal Complexes
Acid catalysis
Silica
Hammett constant
Mesoporosity
Iron complex
Porphyrin(tetraaryl) derivative
Oxidation
Metalloporphyrin
Kinetics
Acetic acid
Chemical synthesis
Electron acceptor
Electron donor
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Summary: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 ρ = 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 ρ = −1.48.
Bibliography:Dedicated to the memory of Professor Yoshihiko Ito (1937−2006).
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ISSN:0022-3263
1520-6904
DOI:10.1021/jo070692a