Catalytic epoxidation of camphene using methyltrioxorhenium(VII) as catalyst

Michel, Typhène; Cokoja, Mirza; Kühn, Fritz E.

doi:10.1016/j.molcata.2012.11.016

Cited by 7 publications

(3 citation statements)

References 29 publications

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“…MTO has been successfully employed as a catalyst in a variety of transformations such as aldehyde olefination, olefin metathesis, and epoxidation of olefins by using of hydrogen peroxide as the oxidant . To date, research interest in MTO and its catalysis remains high. − The benefits of MTO as an epoxidation catalyst are its ease of preparation, broad range of feasible substrates like cycloalkenes, allyl alcohols, and n -alkenes, and its broad activity range in both catalyst loading and reaction conditions . Nevertheless, sensitive epoxides are sometimes found to be catalytically hydrolyzed to the respective diols or follow-up reaction products. − The addition of nitrogen-containing Lewis base ligands often prevents hydrolysis. ,,,− ,, Also the beneficial use of ionic liquids as well as an ionic rhenium(VII) system has recently been explored .…”

Section: Introductionmentioning

confidence: 99%

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Oxidorhenium(V) Complexes with Tetradentate Iminophenolate Ligands: Influence of Ligand Flexibility on the Coordination Motif and Oxygen-Atom-Transfer Activity

et al. 2016

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The synthesis of oxidorhenium(V) complexes 1-3 coordinated by tetradentate iminophenolate ligands H2L1-H2L3 bearing backbones of different rigidity (alkyl, cycloalkyl, and phenyl bridges) allows for the formation of distinct geometric isomers, including a symmetric trans-oxidochlorido coordination motif in complex 3. The complex employing a cycloalkyl-bridged ligand (2) of intermediate rigidity exhibits an interesting solvent- and temperature-dependent equilibrium between a symmetric (trans) isomer and an asymmetric (cis) isomer in solution. The occurrence of a symmetric isomer for 2 and 3 is confirmed by single-crystal X-ray diffraction analysis. Chlorido abstraction from 2 with AgOTf yields the corresponding cationic complex 2a, which does not exhibit an isomeric equilibrium in solution but adopts the isomeric form predominant for 2 in a given solvent. All complexes were, furthermore, employed in three benchmark oxygen-atom-transfer (OAT) reactions, namely, the reduction of perchlorate, the epoxidation of cyclooctene, and OAT from dimethyl sulfoxide (DMSO) to triphenylphosphane (PPh3), to assess the influence of the isomeric structure on the reactivity in these reactions. In perchlorate reduction, a clear structural influence was observed, where the trans arrangement in 3 led to the complete absence of activity. In the epoxidation reaction, all complexes led to comparable epoxide yields, albeit higher catalytic activity but lower overall stability of the catalysts with a trans arrangement was observed. In OAT from DMSO to PPh3, also a clear structural dependence was observed, where the trans complex 3 led to full phosphane conversion with an excess of oxidant, while the cis compound 1 was completely inactive.

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Section: Introductionmentioning

confidence: 99%

“…9−14 The addition of nitrogen-containing Lewis base ligands often prevents hydrolysis. 4,6,7,[10][11][12]14,15 Also the beneficial use of ionic liquids as well as an ionic rhenium(VII) system has recently been explored. 16 However, there is still interest in robust catalyst alternatives.…”

Section: ■ Introductionmentioning

confidence: 99%

Oxidorhenium(V) Complexes with Tetradentate Iminophenolate Ligands: Influence of Ligand Flexibility on the Coordination Motif and Oxygen-Atom-Transfer Activity

et al. 2016

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“…136 MTO, (2,6-dimethylphenyl)trioxorhenium (XTO) and benzimidazole complexes of methyltrioxorhenium were successfully employed for the epoxidation of various alkenes with H 2 O 2 , UHP or t-butyl hydroperoxide. [137][138][139] The ionic liquids were used as additives in the MTO catalyzed epoxidation and it was found that they performed well in suppressing the epoxide ring-opening reaction. 140 4 ] using H 2 O 2 as an oxidant, was reported.…”

Section: Epoxidationmentioning

confidence: 99%

Synthetic utility of metal catalyzed hydrogen peroxide oxidation of C-H, C-C and C=C bonds in alkanes, arenes and alkenes: Recent advances

Wójtowicz‐Młochowska¹

2016

Arkivoc

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This review presents the current state of the art of homogenic and heterogenic oxygen transfer processes using hydrogen peroxide as oxygen source and compounds and complexes of tranisition metals, Fe, V, Cu, Mn, Rh, Mo, Ti, W, Pd, Os, Zr, Cr, Nb, Co, as the catalysts. Based on the reactions of C-H, C-C and C=C bonds in alkanes, arenes and alkenes various mechanisms of the oxygen-transfer processes are discussed and new methodologies for synthesis of alcohols, phenols, aldehydes, ketones, epoxides and carboxylic acids are indicated.

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Catalytic Oxidation of Biorefinery Lignin to Value‐added Chemicals to Support Sustainable Biofuel Production

2014

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Transforming plant biomass to biofuel is one of the few solutions that can truly sustain mankind's long-term needs for liquid transportation fuel with minimized environmental impact. However, despite decades of effort, commercial development of biomass-to-biofuel conversion processes is still not an economically viable proposition. Identifying value-added co-products along with the production of biofuel provides a key solution to overcoming this economic barrier. Lignin is the second most abundant component next to cellulose in almost all plant biomass; the emerging biomass refinery industry will inevitably generate an enormous amount of lignin. Development of selective biorefinery lignin-to-bioproducts conversion processes will play a pivotal role in significantly improving the economic feasibility and sustainability of biofuel production from renewable biomass. The urgency and importance of this endeavor has been increasingly recognized in the last few years. This paper reviews state-of-the-art oxidative lignin depolymerization chemistries employed in the papermaking process and oxidative catalysts that can be applied to biorefinery lignin to produce platform chemicals including phenolic compounds, dicarboxylic acids, and quinones in high selectivity and yield. The potential synergies of integrating new catalysts with commercial delignification chemistries are discussed. We hope the information will build on the existing body of knowledge to provide new insights towards developing practical and commercially viable lignin conversion technologies, enabling sustainable biofuel production from lignocellulosic biomass to be competitive with fossil fuel.

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Catalytic epoxidation of camphene using methyltrioxorhenium(VII) as catalyst

Cited by 7 publications

References 29 publications

Oxidorhenium(V) Complexes with Tetradentate Iminophenolate Ligands: Influence of Ligand Flexibility on the Coordination Motif and Oxygen-Atom-Transfer Activity

Oxidorhenium(V) Complexes with Tetradentate Iminophenolate Ligands: Influence of Ligand Flexibility on the Coordination Motif and Oxygen-Atom-Transfer Activity

Synthetic utility of metal catalyzed hydrogen peroxide oxidation of C-H, C-C and C=C bonds in alkanes, arenes and alkenes: Recent advances

Catalytic Oxidation of Biorefinery Lignin to Value‐added Chemicals to Support Sustainable Biofuel Production

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