Manganese‐Catalyzed Oxidation with Hydrogen Peroxide

Browne, Wesley R.; Böer, Johannes; Pijper, Dirk; Brinksma, Jelle; Hage, Ronald; Feringa, Ben L.

doi:10.1002/9783527632039.ch11

Cited by 8 publications

(4 citation statements)

References 234 publications

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“…The employment of hydrogen peroxide as terminal oxidant for olefin epoxidation is a promising ecofriendly alternative because this reagent is cheap, readily available, safe at usual concentrations (typically ≤30 wt %), and produces only water as byproduct. , However, the reactivity and selectivity of hydrogen peroxide used alone are limited; therefore, additives and catalysts are needed in order to form more reactive intermediate species. Several catalytic systems have been developed, many of which involve transition metals. − Owing to the depletion of metal resources, new catalysts are required that are inexpensive and that are not based on increasingly scarce metals. , Efforts have been made to develop efficient epoxidation catalysts based on Fe and Ti. − Mn is also a good candidate because it is the third most abundant transition metal in the Earth’s crust and is considered to be nontoxic. , Mn is involved in several biological oxidations, which have inspired the conception of biomimetic oxidation catalysts such as porphyrin–Mn, salen–Mn, phthalocyanin–Mn, and triazamacrocycle–Mn. , In spite of the efficiency of these catalysts, their preparation is often difficult and low-yielding. Moreover, because of the homogeneous nature of such catalysts, their loss at the end of the reaction increases the cost and the environmental impact of the process.…”

Section: Introductionmentioning

confidence: 99%

Switchable Alkene Epoxidation/Oxidative Cleavage with H₂O₂/NaHCO₃: Efficient Heterogeneous Catalysis Derived from Biosourced Eco-Mn

Escande

Petit

Garoux

et al. 2015

ACS Sustainable Chem. Eng.

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International audienceA novel Mn-derived catalyst was prepared starting from the biomass of Mn-hyperaccumulating plants growing on metal-rich soils. Recovery of this biomass as value-added ``ecocatalyst'' provides incentives for the development of phytoextraction programs on soils degraded by mining activities. Characterization of the resulting plant-based catalyst Eco-Mn by inductively coupled plasma mass spectrometry (ICP-MS), X-ray diffraction (XRD), X-ray fluorescence spectrometry (XRF), and X-ray photoelectron spectroscopy (XPS) demonstrated the presence of unusual polymetallic complexes of Mn(II) in the catalyst, along with Fe(III). Incorporation of these species into montmorillonite K10 as solid support provided a supported Eco-Mn catalyst, whose properties were investigated for alkene epoxidation with H2O2 (30 wt %)/NaHCO3 (0.2 M) as a green terminal-oxidizing reagent. The supported Eco-Mn catalyst demonstrated a high efficiency for styrene epoxidation, with only 0.31 mol % Mn, a much lower content of Mn than in previously described Mn-derived heterogeneous catalysts. Although Fe was also present in the supported Eco-Mn catalyst, comparison experiments showed that Fe had only a limited role in the catalysis. The water content in the reaction medium had a beneficial effect, increasing the reaction efficiency. The supported Eco-Mn catalyst was recycled four times without any loss of activity. Comparison of its properties to those of heterogeneous catalysts made by incorporation of commercial MnCl2 center dot 4H(2)O and FeCl3 center dot 6H(2)O highlighted the superior catalytic activity of polymetallic species present in the biosourced catalyst. The substrate scope of the method was extended to various alkenes, including bulky natural products which were epoxidized with high yields (up to 99%), sometimes much higher than those obtained with already described Mn-derived heterogeneous catalysts. Finally, by simple adjustments of reaction conditions, the method allowed controlled access to aldehydes by oxidative cleavage of various styrene-derived substrates (up to 93% yield). The method thus constitutes a valuable alternative not only to classical epoxidation reagents but also to oxidative cleavage of styrene-derived molecules, which usually involves toxic and hazardous reagents

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Section: Introductionmentioning

confidence: 99%

Switchable Alkene Epoxidation/Oxidative Cleavage with H₂O₂/NaHCO₃: Efficient Heterogeneous Catalysis Derived from Biosourced Eco-Mn

Escande

Petit

Garoux

et al. 2015

ACS Sustainable Chem. Eng.

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“…Ideally, catalytic oxidation methods based on efficient, safe, and readily applicable “off the shelf” components (i.e., in situ preparation) are desirable for the oxidation of alkenes with H 2 O 2 for practical, economic, and environmental reasons. Their relatively low toxicity and cost and the often high turnover numbers (TONs) that can be achieved position manganese-, − iron-, tungsten-, − and molybdenum-based catalysts at the focus of current attention . Notable examples are the “off the shelf” systems based on molybdenum and tungsten oxides developed by Payne, Venturello, , and Noyori ,, and co-workers and the methyltrioxorhenium (MTO) system developed by Herrmann , and others.…”

Section: Introductionmentioning

confidence: 99%

Oxidation of Alkenes with H₂O₂ by an in-Situ Prepared Mn(II)/Pyridine-2-carboxylic Acid Catalyst and the Role of Ketones in Activating H₂O₂

et al. 2012

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A simple, high yielding catalytic method for the multigram scale selective epoxidation of electron-rich alkenes using near-stoichiometric H2O2 under ambient conditions is reported. The system consists of a Mn(II) salt (<0.01 mol %), pyridine-2-carboxylic acid (<0.5 mol %), and substoichiometric butanedione. High TON (up to 300 000) and TOF (up to 40 s–1) can be achieved for a wide range of substrates with good to excellent selectivity, remarkable functional group tolerance, and a wide solvent scope. It is shown that the formation of 3-hydroperoxy-3-hydroxybutan-2-one from butanedione, and H2O2 in situ, is central to the activity observed.

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“… , Manganese displays appealing properties for catalysis, thanks to its multiple stable oxidation states and its low toxicity . Consequently, the use of manganese in industrial catalytic processes is expected to increase, as a substitute for precious metals or toxic elements. − …”

Section: Introductionmentioning

confidence: 99%

EcoMnOx, a Biosourced Catalyst for Selective Aerobic Oxidative Cleavage of Activated 1,2-Diols

Escande

Lam²,

Grison

et al. 2017

ACS Sustainable Chem. Eng.

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A novel catalyst, EcoMnOx, was prepared from waste biomass of Mn-hyperaccumulating plants. The valorization of this Mn-rich biomass is an alternative to its costly usual disposing and provides a new source of Mn. Extracted metal ions, including Mn 2+ , were oxidized in mild conditions by H 2 O 2 /NaOH to afford EcoMnOx, as a polymetallic oxide material containing from 8.9 to 14.1 wt % Mn. Spectroscopic studies of this material revealed the presence of Mn layered mixed oxides, rich in Mn IV along with Mn III and Mn II species. EcoMnOx catalytic properties were assessed in the aerobic oxidative cleavage of 1,2-diols, under atmospheric pressure of O 2 or air. With only 10 mol % Mn, up to complete conversions were obtained on activated benzylic and allylic diols, with excellent selectivity toward aldehydes or ketones (98− 99%). Moreover, because of its heterogeneous nature, the catalyst can be removed easily by filtration, and reapplied for a minimum of six successive runs without any loss of activity. Finally, E-factor analysis showed the EcoMnOx generates 4 to 17 times less waste compared to classical reagents such as NaIO 4 and Pb(OAc) 4 , respectively, highlighting the sustainable assets of this new heterogeneous catalyst.

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Manganese‐Catalyzed Oxidation with Hydrogen Peroxide

Cited by 8 publications

References 234 publications

Switchable Alkene Epoxidation/Oxidative Cleavage with H₂O₂/NaHCO₃: Efficient Heterogeneous Catalysis Derived from Biosourced Eco-Mn

Switchable Alkene Epoxidation/Oxidative Cleavage with H₂O₂/NaHCO₃: Efficient Heterogeneous Catalysis Derived from Biosourced Eco-Mn

Oxidation of Alkenes with H₂O₂ by an in-Situ Prepared Mn(II)/Pyridine-2-carboxylic Acid Catalyst and the Role of Ketones in Activating H₂O₂

EcoMnOx, a Biosourced Catalyst for Selective Aerobic Oxidative Cleavage of Activated 1,2-Diols

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Manganese‐Catalyzed Oxidation with Hydrogen Peroxide

Cited by 8 publications

References 234 publications

Switchable Alkene Epoxidation/Oxidative Cleavage with H2O2/NaHCO3: Efficient Heterogeneous Catalysis Derived from Biosourced Eco-Mn

Switchable Alkene Epoxidation/Oxidative Cleavage with H2O2/NaHCO3: Efficient Heterogeneous Catalysis Derived from Biosourced Eco-Mn

Oxidation of Alkenes with H2O2 by an in-Situ Prepared Mn(II)/Pyridine-2-carboxylic Acid Catalyst and the Role of Ketones in Activating H2O2

EcoMnOx, a Biosourced Catalyst for Selective Aerobic Oxidative Cleavage of Activated 1,2-Diols

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Switchable Alkene Epoxidation/Oxidative Cleavage with H₂O₂/NaHCO₃: Efficient Heterogeneous Catalysis Derived from Biosourced Eco-Mn

Switchable Alkene Epoxidation/Oxidative Cleavage with H₂O₂/NaHCO₃: Efficient Heterogeneous Catalysis Derived from Biosourced Eco-Mn

Oxidation of Alkenes with H₂O₂ by an in-Situ Prepared Mn(II)/Pyridine-2-carboxylic Acid Catalyst and the Role of Ketones in Activating H₂O₂