Biologically inspired oxidation catalysis using metallopeptides

Vicens, Laia; Costas, Miguel

doi:10.1039/c7dt03657d

Cited by 17 publications

(9 citation statements)

References 96 publications

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“…Over the past four decades, protein-based ArMs have been widely investigated to achieve a variety of valuable enantioselective transformations [1][2][3][4][5][6] . To precisely characterise the active centres and obtain insight into the reaction mechanisms of ArMs, simple scaffolds of peptides and amino acids have been employed to rationally design artificial metallo-peptides [7][8][9][10][11][12][13] and metalloamino acids [14][15][16][17][18][19][20][21] . In recent years, nucleic acids have aroused much interest among chemists for constructing diverse nucleic acid-based ArMs for enantioselective catalysis.…”

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confidence: 99%

A Cu(II)–ATP complex efficiently catalyses enantioselective Diels–Alder reactions

Wang

et al. 2020

Nat Commun

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Natural biomolecules have been used extensively as chiral scaffolds that bind/surround metal complexes to achieve stereoselectivity in catalytic reactions. ATP is ubiquitously found in nature as an energy-storing molecule and can complex diverse metal cations. However, in biotic reactions ATP-metal complexes are thought to function mostly as co-substrates undergoing phosphoanhydride bond cleavage reactions rather than participating in catalytic mechanisms. Here, we report that a specific Cu(II)-ATP complex (Cu2+·ATP) efficiently catalyses Diels-Alder reactions with high reactivity and enantioselectivity. We investigate the substrates and stereoselectivity of the reaction, characterise the catalyst by a range of physicochemical experiments and propose the reaction mechanism based on density functional theory (DFT) calculations. It is found that three key residues (N7, β-phosphate and γ-phosphate) in ATP are important for the efficient catalytic activity and stereocontrol via complexation of the Cu(II) ion. In addition to the potential technological uses, these findings could have general implications for the chemical selection of complex mixtures in prebiotic scenarios.

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confidence: 99%

A Cu(II)–ATP complex efficiently catalyses enantioselective Diels–Alder reactions

Wang

et al. 2020

Nat Commun

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“…[ 13,14 ] Such intermediates are recognized with highly active species for electron and/or oxygen atom transfer mechanism. [ 15 ]…”

Section: Introductionmentioning

confidence: 99%

Polar and nonpolar iron (II) complexes of isatin hydrazone derivatives as effective catalysts in oxidation reactions and their antimicrobial and anticancer activities

El‐Sayed

Adam

2022

Applied Organom Chemis

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Two iron (II) complexes of various derivatives (polar with 5‐sodium sulfoante group and nonpolar with di‐tert butyl groups, HLSO3Na and HLDBu, respectively) of isatin hydrazones were synthesized within 1:2 molar ratios of Fe2+ ion to the isatin hydrazone ligand giving Fe (LSO3Na)2 and Fe (LDBu)2, respectively. The polar and nonpolar isatin hydrazone derivatives behaved as O,N,O‐tridentate pincer chelating agents with Fe2+ ions. The variation in polarity of the two Fe2+‐complexes controlled their catalytic action in the oxidation of alcohols using tBuOOH (tert‐butyl hydroperoxide). The polar catalyst showed more enhanced catalytic behavior than that of the nonpolar one. The optimized conditions for Fe (LDBu)2 was found to be better at 70°C after 4 h with 86% of benzaldehyde than that with Fe (LSO3Na)2 (at 90°C after 2 h with 84% of benzaldehyde). Their kinetic studies were used to derive the thermodynamic parameters of Ea and ΔG# for the catalytic processes.Biologically, based on their high reactivity toward some bacterial and fungal strains and some human cancer cell lines, the calf thymus‐DNA (ctDNA) interaction of the current compounds were studied. The nonpolar Fe2+‐complex (Fe (LDBu)2) assigned more reactivity with ctDNA more than that of the polar reagent (Fe (LSO3Na)2) and also more than that of their uncoordinated ligands depending on their lipophilicity. Their reactivities toward ctDNA was established spectrophotometrically and within the changes in the DNA solution viscosity. The binding strength was evaluated with the magnitudes of the binding constant (Kb = 3.03, 3.21, 9.79, and 11.51 × 108 mol−1 dm3 for HLDBu, HLSO3Na, Fe (LDBu)2, and Fe (LSO3Na)2, respectively), which supported by the Gibbs' free energy values −3.12, −31.42, −34.18, and −34.58 kJ mol−1, respectively.

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“…Natural mononuclear nonheme iron enzymes are involved in metabolically vital oxidative transformations, catalyzing a wide range of chemical reactions with high efficiency, [ 14 ] and the search of synthetic models mimicking Nature is constantly pursued. [ 15 ] In the case of nonheme iron enzymes and their models, key intermediates are high‐valent iron‐oxo intermediates, such as iron(III)‐super‐oxo, iron(III)‐peroxo, iron(III)‐hydroperoxo, and iron(IV)‐ or iron(V)‐oxo species. [ 14a,16 ] While iron(III)‐superoxo species have been recognized as active oxidants in the C–H bond activation and oxygen atom transfer (OAT) reactions although the intermediates are only able to activate weak C–H bonds in hydrocarbons, the reactivities of nonheme iron(III)–hydroperoxo species are still a matter of debate and subject of in‐depth experimental and theoretical investigations.…”

Section: Introductionmentioning

confidence: 99%

“…[ 17 ] On the other hand, nonheme iron(IV)‐oxo species are competent oxidants capable of abstracting hydrogen atom in C–H bond activation reactions. [ 15e ]…”

Section: Introductionmentioning

confidence: 99%

Catalytic Selective Oxidation of Primary and Secondary Alcohols Using Nonheme [Iron(III)(Pyridine‐Containing Ligand)] Complexes

et al. 2020

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The selective oxidation of different primary and secondary alcohols to carbonyl compounds by hydrogen peroxide was found to be catalyzed in conversion ranging from good to excellent by an iron(III) complex of a pyridine‐containing macrocyclic ligand (Pc‐L), without the need of any additive. The choice of the counteranion (Cl, Br, OTf) appeared to be of fundamental importance and the best results in terms of selectivity (up to 99 %) and conversion (up to 98 %) were obtained using the well‐characterized [Fe(III)(Br)2(Pc‐L)]Br complex, 4c. Magnetic moments in solid‐state, also confirmed in solution ([D6]DMSO) by Evans NMR method, were calculated and point out to an iron metal center in the high spin state of 5/2. The crystal structure shows that the iron(III) center is coordinated by the four nitrogen atoms of the macrocycle and two bromide anions to form a distorted octahedral coordination environment. The catalytic oxidation of benzyl alcohol in acetonitrile was found occurring with better conversions and selectivities than in other solvents. The reaction proved to be quite general, tolerating aromatic and aliphatic alcohols, although very low yields were obtained for terminal aliphatic alcohols. Preliminary mechanistic studies are in agreement with a catalytic cycle promoted by a high‐spin iron complex.

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Biologically inspired oxidation catalysis using metallopeptides

Cited by 17 publications

References 96 publications

A Cu(II)–ATP complex efficiently catalyses enantioselective Diels–Alder reactions

A Cu(II)–ATP complex efficiently catalyses enantioselective Diels–Alder reactions

Polar and nonpolar iron (II) complexes of isatin hydrazone derivatives as effective catalysts in oxidation reactions and their antimicrobial and anticancer activities

Catalytic Selective Oxidation of Primary and Secondary Alcohols Using Nonheme [Iron(III)(Pyridine‐Containing Ligand)] Complexes

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