Selenium catalysed oxidations with aqueous hydrogen peroxide. Part I: epoxidation reactions in homogeneous solution

Brink, Gerd‐Jan ten; Fernandes, Bruno C. M.; Vliet, Michiel C. A. van; Arends, Isabel W. C. E.; Sheldon, Roger A.

doi:10.1039/b008198l

Cited by 103 publications

(50 citation statements)

References 38 publications

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“…The reaction was also carried out in the presence of traces of sodium acetate (0.5 mol%) to control the pH of the reaction medium and to minimize the hydrolysis suffered by the epoxide [25][26][27], which can be observed in entries 7 and 8 of Table 4. Although the reaction is slightly slower in these conditions, the hydrolysis was totally avoided.…”

Section: Epoxidation Of Cyclohexenementioning

confidence: 99%

“…Although classically this catalytic system had been dominated by the use of dichloromethane (DCM) and 2,2,2-trifluoroethanol (TFE) as solvents [25][26], it was found that some of the glycerol-derived solvents are as good as TFE in some cases and often better than DCM. The best glycerol-based solvents in this study are all bore short fluorinated chains, see scheme 1.…”

Section: Introductionmentioning

confidence: 99%

“…Moreover diselenides can be easily oxidized in situ by hydrogen peroxide to seleninic acid or peroxyseleninic acid, which are in some cases excellent catalysts in the oxidation of organic compounds [21][22][23][24], as, for instance, epoxidation reaction of alkenes [25], Baeyer-Villiger reaction [26], oxidation of carbonyl compounds [27], dehydrogenation of carbonyl compounds [28][29], oxidation of secondary amines [30][31], oxidation of imines [32], or selenenylations or halogenations [33].…”

Section: Introductionmentioning

confidence: 99%

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Epoxidation of cyclooctene and cyclohexene with hydrogen peroxide catalyzed by bis[3,5-bis(trifluoromethyl)-diphenyl] diselenide: Recyclable catalyst-containing phases through the use of glycerol-derived solvents

García-Marín

Toorn

Mayoral

et al. 2011

Journal of Molecular Catalysis A: Chemical

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A green strategy has been explored for olefin epoxidation which combines renewable solvents (derived from glycerol), aqueous hydrogen peroxide, and catalyst recycling (a seleninic acid derivative). The use of fluorinated glycerol derivatives allows good catalytic activity in the epoxidation of cyclooctene and cyclohexene with aqueous hydrogen peroxide, preventing epoxide hydrolysis to a great extent, which is particularly remarkable in the case of cyclohexene. Furthermore, recycling of the catalytically active phase is possible through distillation of the cyclohexene oxide from the reaction mixture, which can be subsequently recharged with fresh oxidant and substrate.

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Section: Epoxidation Of Cyclohexenementioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Epoxidation of cyclooctene and cyclohexene with hydrogen peroxide catalyzed by bis[3,5-bis(trifluoromethyl)-diphenyl] diselenide: Recyclable catalyst-containing phases through the use of glycerol-derived solvents

García-Marín

Toorn

Mayoral

et al. 2011

Journal of Molecular Catalysis A: Chemical

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“…In the presence of 1 mol % of phenylarsonic acid (5), quantitative conversion to the epoxide 4 is achieved within ca. 4 h, whereas < 10% conversion occurs in the absence of the arsonic acid catalyst [Scheme 1, Equations (2) and (3)].…”

Section: Introductionmentioning

confidence: 99%

Kinetic Studies of Olefin Epoxidation with Hydrogen Peroxide in 1,1,1,3,3,3‐Hexafluoro‐2‐propanol Reveal a Crucial Catalytic Role for Solvent Clusters

Berkessel

Adrio

2004

Adv Synth Catal

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The epoxidation of cyclooctene and 1-octene with hydrogen peroxide was studied kinetically in HFIP (1,1,1,3,3,3-hexafluoro-2-propanol)/1,4-dioxane mixtures. In the case of cyclooctene, no additional catalyst was applied, whereas the epoxidation of 1-octene was run in the presence of phenylarsonic acid as catalyst. For both reaction types, two kinetic regimes can be distinguished: at low HFIP concentration (n HFIP /n total X0.15), both the catalyzed and the uncatalyzed reaction show first order dependence on the HFIP concentration. This result is interpreted by the HFIP ™charge template∫ for the uncatalyzed epoxidation (as postulated by Shaik and Neumann) and by the formation of an arsonic acid mono-HFIP ester for the catalyzed reaction. At high HFIP concentration (n HFIP /n total x0.5), both reaction types are up to ca. 5 orders of magnitude faster and show ca. 12 th order dependence on the HFIP concentration. We propose that the dramatic accelerations observed at high HFIP concentrations are brought about by HFIP clusters. Based on literature data (Fioroni, Roccatano, Hong, Suhm), it is concluded that the epoxidation reactions studied here take place in a HFIP coordination sphere comprising ca. 12 HFIP molecules, and that this coordination sphere effects the enormous increases in epoxidation rates. This mechanistic model bears resemblance to enzymatic reactions taking place in and being catalyzed by a protein matrix.

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“…12 However, this system required the use of the bis(3,5-bis(trifluoromethyl)phenyl) diselenide (ArSe 2 ), which is not commercially available and must be prepared using the procedure reported by ten Brink. 13 The optimized system also employs urea-hydrogen peroxide as oxidant (water must to be excluded from this process to prevent hydrolysis of the parent imine). We began our studies using commercially available diphenyldiselenide (5 mol%) and aqueous hydrogen peroxide (50%, 3.0 equiv.)…”

Section: Methodsmentioning

confidence: 99%

Activation of Hydrogen Peroxide by Diphenyl Diselenide for Highly Enantioselective Oxaziridinium Salt Mediated Catalytic Asymmetric Epoxidation

Buckley

Elliott

Chan

et al. 2013

Synlett

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The first reported use of benzeneperseleninic acid as a catalytic mediator for oxaziridinium ion catalysed epoxidation is described, providing reaction rates and ee values (up to 85%) similar to those reported when using oxone as the stoichiometric oxidant. A dual catalytic cycle is proposed, in which diphenyl diselenide is initially converted into the perseleninic acid, which in turn oxidises an iminium ion to the corresponding oxaziridinium species, thus facilitating asymmetric oxygen transfer to an alkene.

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Selenium catalysed oxidations with aqueous hydrogen peroxide. Part I: epoxidation reactions in homogeneous solution

Cited by 103 publications

References 38 publications

Epoxidation of cyclooctene and cyclohexene with hydrogen peroxide catalyzed by bis[3,5-bis(trifluoromethyl)-diphenyl] diselenide: Recyclable catalyst-containing phases through the use of glycerol-derived solvents

Epoxidation of cyclooctene and cyclohexene with hydrogen peroxide catalyzed by bis[3,5-bis(trifluoromethyl)-diphenyl] diselenide: Recyclable catalyst-containing phases through the use of glycerol-derived solvents

Kinetic Studies of Olefin Epoxidation with Hydrogen Peroxide in 1,1,1,3,3,3‐Hexafluoro‐2‐propanol Reveal a Crucial Catalytic Role for Solvent Clusters

Activation of Hydrogen Peroxide by Diphenyl Diselenide for Highly Enantioselective Oxaziridinium Salt Mediated Catalytic Asymmetric Epoxidation

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