Mimicking P450 processes and the use of
                    metalloporphyrins

Simões, Mário M. Q.; Neves, Cláudia M. B.; Pires, Sónia M. G.; Neves, Maria G. P. M. S.; Cavaleiro, José A. S.

doi:10.1351/pac-con-12-11-15

Cited by 40 publications

(26 citation statements)

References 100 publications

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“…In particular, iron-porphyrins have been the subject of extensive reviews, due to their biological relevance as part of cytochrome P450 [14,15], with their use as catalysts in epoxidation reactions being highlighted on many occasions [16]. On the other hand, the efficiency of the Jacobsen-Katsuki epoxidation prompted the study of Mn(salen), which is much more focused on their catalytic activity towards the epoxidation of alkenes.…”

Section: Introduction and Contextmentioning

confidence: 99%

Strengths, Weaknesses, Opportunities and Threats: Computational Studies of Mn- and Fe-Catalyzed Epoxidations

Teixeira

Cordeiro

2016

Catalysts

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Abstract:The importance of epoxides as synthetic intermediates in a number of highly added-value chemicals, as well as the search for novel and more sustainable chemical processes have brought considerable attention to the catalytic activity of manganese and iron complexes towards the epoxidation of alkenes using non-toxic terminal oxidants. Particular attention has been given to Mn(salen) and Fe(porphyrin) catalysts. While the former attain remarkable enantioselectivity towards the epoxidation of cis-alkenes, the latter also serve as an important model for the behavior of cytochrome P450, thus allowing the exploration of complex biological processes. In this review, a systematic survey of the bibliographical data for the theoretical studies on Mn-and Fe-catalyzed epoxidations is presented. The most interesting patterns and trends are reported and finally analyzed using an evaluation framework similar to the SWOT (Strengths, Weaknesses, Opportunities and Threats) analysis performed in enterprise media, with the ultimate aim to provide an overview of current trends and areas for future exploration.

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Section: Introduction and Contextmentioning

confidence: 99%

Strengths, Weaknesses, Opportunities and Threats: Computational Studies of Mn- and Fe-Catalyzed Epoxidations

Teixeira

Cordeiro

2016

Catalysts

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“…Given the recent interest in heterogeneous catalysis for the oxidation of ␤-IP [4,12,14,52] and the large number of studies demonstrating the efficacy of porphyrin oxidation catalysts [53][54][55][56] it is reasonable to suggest that MTPPs may be immobilized to find more efficient catalysts. Heterogeneous compounds are easy to separate and reuse for cleaner and more efficient chemical reactions.…”

Section: Resultsmentioning

confidence: 99%

Aerobic oxidation of β-isophorone by tetraphenylporphyrin catalysts in pyridine solution

Burns

Huang

Weare

et al. 2015

Journal of Molecular Catalysis A: Chemical

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a b s t r a c tA kinetic study was conducted using five metallo-tetraphenylporphyrins (MTPPs) as catalysts for the aerobic oxidation reaction of ␤-isophorone (␤-IP) to ketoisophorone (KIP). The oxidation reaction catalyzed by MTPPs (M = Cr, Mn, Fe, Co and Cu) was observed over a seven hour period under a range of experimental conditions. Changes in the specificity of conversion of reactant to the product, KIP, and the main side-product, ␣-isophorone (␣-IP), were observed at temperatures ranging from 60 • C to 75 • C, in solvents with varying compositions of pyridine and ␤-IP, with different MTPP catalysts, oxygen gas flow rates, and solution agitation frequencies. Control experiments show that MTPP catalysts modestly increase the rate of KIP formation, but significantly improve specificity through the apparent suppression of ␣-IP formation. Analysis revealed that MnTPP (CH 3 COO − ) produced the highest product specificity ratio [KIP]/ [␣-IP]. Given that all of the metals were in the 3+ oxidation state in this study and there was no observed binding by O 2 to any of the MTPP catalysts, the catalytic mechanism is suggested to involve the binding of ␤-IP to the MTPP metal center. Binding of ␤-IP is most favorable when pyridine is the trans ligand, but ␤-IP is also observed to weakly bind when trans to acetate in the MnTPP adduct. This conclusion is supported by electronic absorption spectroscopy, resonance Raman spectroscopy and density functional theory (DFT) calculations. The role played by the catalyst appears to be the activation of hydrogen abstraction following the substrate's ligation to the metal, rather than the more traditional role of MTPPs as O 2 activation catalysts by ligation of diatomic O 2 . ␤-IP oxidation is an example of a case where the catalyst appears to have a more important role for improving the specificity of the reaction (through decreasing side-product formation) rather than increasing the rate of product formation.

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“…Metalloporphyrins are effective and well-known biomimetic catalysts of the cytochrome P450 (CYP450) enzymes in the oxidation of several organic compounds [1][2][3][4][5][6][7][8][9][10][11]. The first porphyrinic model system for alkenes' epoxidation and alkanes' hydroxylation was reported by Groves by using the iron(III) complex of 5,10,15,20-tetraphenylporphyrin (CAT-1) as the catalyst and iodosylbenzene (PhIO) as the oxygen atom donor [12].…”

Section: Introductionmentioning

confidence: 99%

Second-Generation Manganese(III) Porphyrins Bearing 3,5-Dichloropyridyl Units: Innovative Homogeneous and Heterogeneous Catalysts for the Epoxidation of Alkenes

et al. 2019

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The synthesis, characterisation and homogeneous catalytic oxidation results of two manganese(III) porphyrins of the so-called second-generation of metalloporphyrin catalysts, containing one or four 3,5-dichloropyridyl substituents at the meso positions are reported for the first time. The catalytic efficiency of these novel manganese(III) porphyrins was evaluated in the oxidation of cyclooctene and styrene using aqueous hydrogen peroxide as the oxidant, under homogeneous conditions. High conversions were obtained in the presence of both catalysts, obtaining the corresponding epoxide as the major product. The asymmetric metalloporphyrin, chloro[5,10,15-tris(2,6-dichlorophenyl)-20-(3,5-dichloropyridin-4-yl)porphyrinate]manganese(III), CAT-4, evidences a similar activity to that obtained with the well-known and highly efficient second-generation metalloporphyrin catalyst, chloro[5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrinate]manganese(III), CAT-2. CAT-4 was covalently attached onto Merrifield resin and 3-bromopropylsilica supports. The solid materials obtained were characterized by several techniques including diffuse reflectance, UV—VIS spectrophotometry, SEM and XPS. The catalytic results for the oxidation of cyclooctene and styrene using the immobilized catalysts are also presented. The Merrifield-supported catalyst showed to be very efficient, leading to five catalytic cycles in the oxidation of cyclooctene, using tert-butyl hydroperoxide as the oxidant.

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Mimicking P450 processes and the use of metalloporphyrins

Cited by 40 publications

References 100 publications

Strengths, Weaknesses, Opportunities and Threats: Computational Studies of Mn- and Fe-Catalyzed Epoxidations

Strengths, Weaknesses, Opportunities and Threats: Computational Studies of Mn- and Fe-Catalyzed Epoxidations

Aerobic oxidation of β-isophorone by tetraphenylporphyrin catalysts in pyridine solution

Second-Generation Manganese(III) Porphyrins Bearing 3,5-Dichloropyridyl Units: Innovative Homogeneous and Heterogeneous Catalysts for the Epoxidation of Alkenes

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