Oxoferryl Porphyrin/Hydrogen Peroxide System Whose Behavior is Equivalent to Hydroperoxoferric Porphyrin

Kitagishi, Hiroaki; Tamaki, Mariko; Ueda, Takunori; Hirota, Shun; Ohta, Takao; Naruta, Yoshinori; Kawasaki, Koji

doi:10.1021/ja106798a

Cited by 44 publications

(33 citation statements)

References 25 publications

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“…The inclusion of porphyrin with a cyclodextrin dimer (Py3CD or Py3OCD, Figure ) prevents the unspecific oxidative decomposition of the porphyrin ring caused by CHPO. The absorption spectrum ( λ max at 422 and 558 nm) was quite similar to that of O=Fe IV PCD1, indicating the formation of O=Fe IV PCD3 in the reaction of met‐hemoCD3 with CHPO.…”

Section: Resultsmentioning

confidence: 77%

“…We previously reported the formation of a stable Cpd II‐like O=Fe IV P [P= meso ‐tetrakis(4‐sulfonatophenyl)porphyrin dianion] complex in aqueous solution containing a cyclodextrin dimer, and its intramolecular oxo‐transfer reaction (Figure ) . We utilized the supramolecular complex met‐hemoCD1 (Figure a) that was composed of meso ‐tetrakis(4‐sulfonatophenyl)porphinatoiron(III) (Fe III TPPS) and a per‐ O ‐methylated β‐cyclodextrin dimer with an ‐SCH 2 PyCH 2 S‐ (Py=pyridine‐3,5‐diyl) linker (Py3CD, Figure a) .…”

Section: Introductionmentioning

confidence: 99%

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Intramolecular Oxidative O‐Demethylation of an Oxoferryl Porphyrin Complexed with a Per‐O‐methylated β‐Cyclodextrin Dimer

Kitagishi

Kurosawa

Kawasaki

2016

Chemistry An Asian Journal

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The intramolecular oxidation of ROCH to ROCH OH, where the latter compound spontaneously decomposed to ROH and HCHO, was observed during the reaction of the supramolecular complex (met-hemoCD3) with cumene hydroperoxide in aqueous solution. Met-hemoCD3 is composed of meso-tetrakis(4-sulfonatophenyl)porphinatoiron(III) (Fe TPPS) and a per-O-methylated β-cyclodextrin dimer having an -OCH PyCH O- linker (Py=pyridine-3,5-diyl). The O=Fe TPPS complex was formed by the reaction of met-hemoCD3 with cumene hydroperoxide, and isolated by gel-filtration chromatography. Although the isolated O=Fe TPPS complex in the cyclodextrin cage was stable in aqueous solution at 25 °C, it was gradually converted to Fe TPPS (t =7.6 h). This conversion was accompanied by oxidative O-demethylation of an OCH group in the cyclodextrin dimer. The results indicated that hydrogen abstraction by O=Fe TPPS from ROCH yields HO-Fe TPPS and ROCH . This was followed by radical coupling to afford Fe TPPS and ROCH OH. The hemiacetal (ROCH OH) immediately decomposed to ROH and HCHO. This study revealed the ability of oxoferryl porphyrin to induce two-electron oxidation.

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Section: Resultsmentioning

confidence: 77%

Section: Introductionmentioning

confidence: 99%

Intramolecular Oxidative O‐Demethylation of an Oxoferryl Porphyrin Complexed with a Per‐O‐methylated β‐Cyclodextrin Dimer

Kitagishi

Kurosawa

Kawasaki

2016

Chemistry An Asian Journal

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“…Peroxyacids 26,[32][33][34][35] , hydroperoxides [36][37][38][39] or inorganic salts [40][41][42][43][44][45] were generally employed as terminal oxidants in mechanistic studies, and the reactions were always performed in water or mixed solvents (such as CH 3 OH/H 2 O or CH 3 CN/H 2 O). In fact, PhIO is often mechanistically cleaner than these alternatives 46 .…”

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confidence: 99%

Spectroscopic observation of iodosylarene metalloporphyrin adducts and manganese(V)-oxo porphyrin species in a cytochrome P450 analogue

Guo

Dong

et al. 2012

Nat Commun

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Different metalloporphyrin model compounds have been synthesized to study the mechanisms of cytochrome P450s with various terminal oxidants, and numerous intermediates have been reported. However, the detailed mechanism of the oxygen atom transfer from iodosylarene to the substrates remains unclear. Here we report the direct ultraviolet-visible spectroscopic observation of the soluble iodosylarene-manganese porphyrin adduct following catalytic oxidation using 2,4,6-tri-tert-butylphenol as the reductant. When the reductant is changed to cisstilbene, the rate-determining step also changes. Both the iodosylarene-manganese porphyrin adduct and [(porphyrin)Mn(V) ¼ O] species may be simultaneously observed. In the absence of reductant, the adduct of iodosylarene with sterically hindered [Mn(meso-tetrakis(2,6-dichlorophenyl)porphinato)Cl] is immediately formed, and smoothly converted into a highvalent [(porpyrinato)Mn ¼ O]. Electrospray ionization mass spectrometry analysis of the reaction further confirms the transformation between these species. This study provides an insight into the mechanism of oxygen transfer within the haem-containing enzymatic systems.

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“…CDs are capable of forming inclusion complexes with many guest species such as a drug in both aqueous solution and the solid state has been widely exploited. [23][24][25][26] The major driving forces of the formation of CD inclusion compounds are hydrophobic and van der Waals interactions between the inner surface of the CD ring and the hydrophobic sites on the guest. In an aqueous solution, the complexes are readily dissociated, and free drug molecules are in relatively rapid dynamic equilibrium with drug molecules bound within the CD cavity.…”

Section: Drug-cd Complex Formation: the Unique Abilitymentioning

confidence: 99%

Computer‐aided drug design to explore cyclodextrin therapeutics and biomedical applications

Abdolmaleki

Ghasemi

2017

Chem Biol Drug Des

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Cyclodextrin (CD) is a subset of the macrocyclic structural class, which is an important class of small organic agents that are useful functional excipients. They have wide range application possibilities in different fields of sciences such as material preparation, medicine, analytical chemistry, and separation processes. They are used widely in pharmaceutical formulations and drug delivery for increasing the water solubility of low soluble drugs and drug candidates. Due to the ring structure, they behave differently than smaller molecules and may be capable of hitting new classes of targets. A macrocyclic molecule presents varied functionality and stereochemical complexity in a pre-organized conformation of the ring structure. This can result in high selectivity and affinity for protein targets while conserving enough bioavailability to arrive at intracellular locations. Regardless of these valuable features, and the verified success of several marketed macrocycle drugs isolated from natural compounds, this class has been little explored in drug development. This study describes some of the key features of the CDs therapeutic discovery. Also, the application of computational chemistry approaches such as QSAR/QSPR, molecular docking, and molecular/quantum mechanics for modeling of CD-drug system is reviewed briefly. K E Y W O R D Sbioavailability, computational, cyclodextrin, drug design, drug discovery, macrocyclic, therapeutic

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Oxoferryl Porphyrin/Hydrogen Peroxide System Whose Behavior is Equivalent to Hydroperoxoferric Porphyrin

Cited by 44 publications

References 25 publications

Intramolecular Oxidative O‐Demethylation of an Oxoferryl Porphyrin Complexed with a Per‐O‐methylated β‐Cyclodextrin Dimer

Intramolecular Oxidative O‐Demethylation of an Oxoferryl Porphyrin Complexed with a Per‐O‐methylated β‐Cyclodextrin Dimer

Spectroscopic observation of iodosylarene metalloporphyrin adducts and manganese(V)-oxo porphyrin species in a cytochrome P450 analogue

Computer‐aided drug design to explore cyclodextrin therapeutics and biomedical applications

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