Biomimetic oxygenations catalyzed by metalloporphyrins and metalloporphinoids bearing co-catalytic functions

Abstract

Abstract

Periodate-Mediated Aerobic Oxidation of Sulfides over a Bifunctional Porphyrin-polyoxometalate Catalyst: Photosensitized Singlet Oxygen Oxidation of Iodate to Periodate

“…The oxidation of organic compounds with periodate on tungsten polyoxometalate (POM) is the first report on the activation of periodate by d 0 transition metals. It is noteworthy that the presence of a cocatalyst (imidazoles or pyridines) was most often necessary to achieve an acceptable conversion value in the oxidation of organic substrates catalyzed by metalloporphyrins and metal Schiff base complexes. − Also, in the case of the d n transition-metal complexes, the formation of high-valent metal oxo species with higher oxidizing ability than the corresponding six-coordinate periodato intermediates ,,− led to the overoxidation of organic substrates such as sulfides and a decrease in the selectivity of the reaction toward sulfoxides. As shown in various studies, ,,, the formation of high-valent metal oxo species is significantly facilitated in water and organic solvents containing water or hydrogen-bond donors such as alcohols.…”

Mechanistic Study for the Facile Oxidation of Trimethoprim on a Manganese Porphyrin Incorporated Glassy Carbon Electrode

“…Many different supramolecular architectures based on porphyrin–substrate complexes are used for molecular recognition purposes, as receptors and sensors. Utilization of porphyrins in catalysis is also based on their ability to bind substrates. − Several experimental and computational works have been performed on oxidative catalysis by metalloporphyrin, especially Mn(III) and Fe(III). − DFT computational approaches have afforded an important new tool for assessing the roles of axial ligation, spin state crossings, and charge distribution in the metalloporphyrin-catalyzed reaction. , …”

Kinetics of redox mediator tris(4-bromophenyl)amine in acetonitrile and ionic liquid [BMIm][PF6]: Oxidation of benzyl and cyclohexyl alcohols

“…Selective oxidation of a variety of organic substrates by electrochemically generated stable radical-cations of 2,2,6,6-tetramethyl piperidine-1-oxyl (TEMPO), metalloporphyrins, phthalocyanines and triphenylamines are known to be useful mediators in electroorganic synthesis [1][2][3][4][5][6]. In this respect, the electrogenerated psubstituted triphenylamine radical-cation is a versatile candidate for the catalytic oxidation of alcohols [7,8], side-chain oxidation of alkyl aromatic compounds [9] and benzylic ethers [10].…”