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Development of Biomimetic Catalytic Systems for Selective Oxidations with H2O2 and O2
Stockholm University, Faculty of Science, Department of Organic Chemistry.
2008 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Four different catalytic systems were studied for biomimetic coupled oxidations using H2O2 or O2. In the first example, osmium tetroxide works as a substrate-selective catalyst for dihydroxylation of olefins. Electron transfer to H2O2 is facilitated by electron transfer mediators (ETMs). In one case VO(acac)2 or MeReO3 was used as ETM; in the other case a combination of flavin and tertiary amine was used as ETMs. These three systems were immobilized in the ionic liquid [bmim]PF6 for the purpose of recycling of the catalyst.

In the second example, an organocatalyst (a flavin) was used for the oxidation of sulfides to sulfoxides and this catalytic system was recycled and reused in an ionic liquid.

In the third example, primary aromatic amines were oxidized by H2O2 to nitroso compounds in a selenium-catalyzed oxidation. The nitrosoarenes were used in a one-pot hetero Diels-Alder reaction with dienes forming 1,2-oxazines.

In the fourth example, a cobalt salophen complex was immobilized in different zeolites. The catalyst was used in aerobic oxidation of p-hydroquinone and the zeolite catalyst could be reused. The oxidative carbocyclization of ene-allenes was tested successfully using the triple catalytic system consisting of palladium(II), p-benzoquinone, and the immobilized catalyst for O2 activation.

All these systems gave mild and selective oxidations with environmentally friendly and inexpensive terminal oxidants.

Place, publisher, year, edition, pages
Department of Organic Chemistry , 2008. , 66 p.
Keyword [en]
Biomimetic oxidations, catalyst immobilization, dihydroxylation, sulfoxidation, flavin
National Category
Chemical Sciences
Research subject
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-7502ISBN: 978-91-7155-646-2 (print)OAI: oai:DiVA.org:su-7502DiVA: diva2:198441
Public defence
2008-05-15, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 12 A, Stockholm, 13:00
Opponent
Supervisors
Available from: 2008-04-24 Created: 2008-04-24Bibliographically approved
List of papers
1. Ionic liquid-immobilized catalytic system for biomimetic dihydroxylation of olefins
Open this publication in new window or tab >>Ionic liquid-immobilized catalytic system for biomimetic dihydroxylation of olefins
2004 In: Chemical Communication, ISSN 0366-5607, no 13, 1494-1495 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-24863 (URN)
Note
Part of urn:nbn:se:su:diva-7502Available from: 2008-04-24 Created: 2008-04-24Bibliographically approved
2. Osmium-catalyzed dihydroxylation of alkenes by H2O2 in room temperature ionic liquid co-catalyzed by VO(acac)2 or MeReO3
Open this publication in new window or tab >>Osmium-catalyzed dihydroxylation of alkenes by H2O2 in room temperature ionic liquid co-catalyzed by VO(acac)2 or MeReO3
2005 In: Journal of organometallic chemistry, ISSN 0022-328X, Vol. 690, no 15, 3614-3619 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-24864 (URN)
Note
Part of urn:nbn:se:su:diva-7502Available from: 2008-04-24 Created: 2008-04-24Bibliographically approved
3. Efficient and Selective Sulfoxidation by Hydrogen Peroxide, Using a Recyclable Flavin-[bmim]PF6 Catalytic System
Open this publication in new window or tab >>Efficient and Selective Sulfoxidation by Hydrogen Peroxide, Using a Recyclable Flavin-[bmim]PF6 Catalytic System
2006 In: Journal of organic chemistry, ISSN 0022-3263, Vol. 71, no 10, 3849 -3853 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-24865 (URN)
Note
Part of urn:nbn:se:su:diva-7502Available from: 2008-04-24 Created: 2008-04-24Bibliographically approved
4. In Situ Generation of Nitroso Compounds from Catalytic Hydrogen Peroxide Oxidation of Primary Aromatic Amines and Their One-Pot Use in Hetero-Diels–Alder Reactions
Open this publication in new window or tab >>In Situ Generation of Nitroso Compounds from Catalytic Hydrogen Peroxide Oxidation of Primary Aromatic Amines and Their One-Pot Use in Hetero-Diels–Alder Reactions
2007 In: European journal of organic chemistry, ISSN 1434-193X, no 26, 4431–4436- p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-24866 (URN)000249797200018 ()
Note
Part of urn:nbn:se:su:diva-7502Available from: 2008-04-24 Created: 2008-04-24Bibliographically approved
5. Aerobic Oxidations Catalyzed by Zeolite-Encapsulated Cobalt Salophen
Open this publication in new window or tab >>Aerobic Oxidations Catalyzed by Zeolite-Encapsulated Cobalt Salophen
2008 (English)In: Advanced Synthesis and Catalysis, ISSN 1615-4150, E-ISSN 1615-4169, Vol. 350, no 11-12, 1807-1815 p.Article in journal (Refereed) Published
Abstract [en]

Cobalt salophen was encapsulated in a series of zeolites with a wide variation of the silicon-to-aluminium atomic ratio and with different cations. The zeolite-cobalt salophen catalysts were prepared using the “ship-in-a-bottle technique” where the complex was synthesized in the super cage of the zeolite and therefore locked into the pocket. The encapsulated catalysts were then tested in the aerobic oxidation of hydroquinone to p-benzoquinone; the best encapsulated catalyst was shown to be an efficient electron-transfer mediator in a palladium-catalyzed aerobic oxidative carbocyclization.

Keyword
aerobic oxidation, cobalt salophen, nanostructures, zeolite
National Category
Chemical Sciences
Identifiers
urn:nbn:se:su:diva-24867 (URN)10.1002/adsc.200800294 (DOI)000258503600021 ()
Available from: 2008-04-24 Created: 2008-04-24 Last updated: 2012-02-24Bibliographically approved

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