Isolation, Synthesis and Biomimetic Reactions of Metalloporphyrinoids in Ionic Liquids

Chemoselective epoxidation of electron rich and electron deficient olefins catalyzed by meso-tetraarylporphyrin iron(iii) chlorides in imidazolium ionic liquids

“…3,23,24 The high yields of the different epoxides in ILs can be attributed to the stabilization of the highly charged iron-peroxo or oxo intermediates (compound I of cytochrome P450) generated during the reaction. [15][16][17][18][19][20] The formation of the epoxide (2a) at the electron deficient olefin can be attributed to the formation of ferric peroxo complexes (9). [25][26][27] The reaction of H 2 O 2 and TAPFe(III)Cl forms 8 which equilibrate to 9, depending on the substituents on the phenyl ring of porphyrins as well as axial ligands (Scheme 2).…”

“…9 Room-temperature ionic liquids (RTILs) are potentially environmentally benign solvents for various organic and biochemical transformations. [9][10][11][12][13][14][15][16][17] The hydrophilicity, hydrophobicity, Lewis acidity, viscosity and density of the ILs can be changed by the choice of organic cation, inorganic anion, and the length of the alkyl chain attached to the ILs. [9][10][11][12][13][14][15][16][17] The ILs have been used in organocatalysis along with Lewis acids, Lewis bases, Brønsted acids and Brønsted bases.…”

“…[18][19][20] Metalloporphyrinoids have been used as catalysts to mimic the various reactions of heme enzymes and proteins in imidazolium ILs. 9 In order to understand the role of meso substituents, reaction media and oxidants on the epoxidation of electron rich and electron deficient olefins, we have examined the epoxidation of substrates containing both the electron rich and electron deficient olefins within a single molecule, with different monooxygen donors catalyzed by 5,10,15,20-tetraaryliron(III) porphyrins in imidazolium ILs.…”

Efficient oxidation of polycyclic aromatic hydrocarbons with H2O2 catalyzed by 5,10,15-triarylcorrolatoiron (IV) chloride in ionic liquids

“…The tedious isolation and fragility of natural cytochrome P450 enzyme system are the main limiting factors for the development of their use at large scale. In this regard, metalloporphyrins have been extensively used in various biomimetic reactions to understand the reaction mechanism and to isolate the metabolites in sufficient amount for further biological studies [3][4][5].…”

“…The use of H 2 O 2 as a clean and mild oxidant in biomimetic oxidation processes is of particular interest because it leads to formation of only water as the side product formed by the dissociation of hydroperoxo complex (Fe IV \O\OH) [9]. Ionic liquids (ILs) have been used as a novel reaction media for various organic syntheses and transformations [4,5]. The positive effect of ILs on oxidation processes using iron and iron complexes has also been reported in literature [10,11].…”