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Biomimetic Reactions: Water Oxidation and Aerobic Oxidation
Stockholm University, Faculty of Science, Department of Organic Chemistry.
2009 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis deals mainly with two oxidation reactions: water oxidation and aerobic oxidation, both of which have been applied in a biomimetic fashion. In the former reaction molecular oxygen is generated whereas in the latter it was used as terminal oxidant in oxidation reactions.

The first part of this thesis describes the synthesis of different ruthenium and manganese complexes that could potentially act as catalysts for water oxidation. This part includes a discussion of the stability and reactivity of a new manganese(III) amide-type complex, that has been used as a catalyst for both epoxidation of stilbene and alcohol oxidation.

The second part of this thesis discusses the synthesis of two new hybrid catalysts consisting of hydroquinone linked cobalt(II) salophen and cobalt(II) salmdpt, which have been used as oxygen-activating catalysts in aerobic oxidation reactions. The former catalyst was applied to the Pd-catalyzed reactions such as 1,4-diacetoxylation of cyclohexadiene whereas the latter was applied to the Ru-catalyzed oxidation of secondary alcohols to ketones. Moreover, these two hybrid catalysts could be used in the Pd-catalyzed carbocyclization of enallenes. In all cases molecular oxygen was used as the stoichiometric oxidant.

 

Place, publisher, year, edition, pages
Stockholm: Department of Organic Chemistry, Stockholm University , 2009. , 57 p.
Keyword [en]
Cobalt(II) salophen, oxygen-activating catalyst, hybrid, manganese complex, epoxidation, water oxidation.
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-26259ISBN: 978-91-7155-844-2 (print)OAI: oai:DiVA.org:su-26259DiVA: diva2:208205
Public defence
2009-04-22, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 12 A, Stockholm, 10:00 (English)
Opponent
Supervisors
Available from: 2009-04-02 Created: 2009-03-16 Last updated: 2011-12-02Bibliographically approved
List of papers
1. A New Square Planar Mn(III) Complex for Catalytic Epoxidation of Stilbene
Open this publication in new window or tab >>A New Square Planar Mn(III) Complex for Catalytic Epoxidation of Stilbene
2008 (English)In: Journal of Organometallic Chemistry, ISSN 0022-328X, E-ISSN 1872-8561, Vol. 693, 1150-1153 p.Article in journal (Refereed) Published
Keyword
Epoxidation, manganese, oxidation of alcohols
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-26344 (URN)10.1016/j.jorganchem.2008.01.009 (DOI)
Available from: 2009-03-19 Created: 2009-03-19 Last updated: 2017-12-13Bibliographically approved
2. An Efficient and Selective Oxidation of Alcohols to Carbonyl Compounds and Carboxylic Acids Catalyzed by A Dinuclear Ruthenium Complex Using Iodosobenzene as Terminal Oxidant
Open this publication in new window or tab >>An Efficient and Selective Oxidation of Alcohols to Carbonyl Compounds and Carboxylic Acids Catalyzed by A Dinuclear Ruthenium Complex Using Iodosobenzene as Terminal Oxidant
2009 (English)In: European Journal of Organic Chemistry, ISSN 1434-193X, E-ISSN 1099-0690Article in journal (Refereed) Submitted
Identifiers
urn:nbn:se:su:diva-26523 (URN)
Available from: 2009-04-01 Created: 2009-04-01 Last updated: 2017-12-13Bibliographically approved
3. Synthesis of new hybrid hydroquinone/cobalt Schiff base catalysts: efficient electron-transfer mediators in aerobic oxidation
Open this publication in new window or tab >>Synthesis of new hybrid hydroquinone/cobalt Schiff base catalysts: efficient electron-transfer mediators in aerobic oxidation
Show others...
2008 (English)In: Chemistry: a European journal, ISSN 0947-6539, Vol. 14, no 25, 7500-7503 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-14632 (URN)doi:10.1002/chem.200800657 (DOI)000259079400011 ()
Available from: 2009-01-02 Created: 2009-01-02 Last updated: 2011-01-10Bibliographically approved
4. Efficient synthesis of hybrid (hydroquinone-Schiff base)cobalt oxidation catalysts
Open this publication in new window or tab >>Efficient synthesis of hybrid (hydroquinone-Schiff base)cobalt oxidation catalysts
Show others...
2009 (English)In: European Journal of Organic Chemistry, ISSN 1434-193X, E-ISSN 1099-0690, no 23, 3973-3976 p.Article in journal (Refereed) Published
Abstract [en]

Hybrid catalysts A and B have recently been found to efficiently transfer electrons from a metal catalyst to molecular oxygen in biomimetic oxidations. In the present work hybrid catalysts A and B were synthesized in high yield from inexpensive starting materials. The key step is an efficient Suzuki cross-coupling, which allows the use of unprotected aldehyde 5. The new synthesis of the title hybrid catalysts is easy to carry out and can be scaled up.

Keyword
Hybrid catalyst, Oxidation, ­Biomimetic oxidation, Electron transfer, Catalyst synthesis, Cross coupling
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-30437 (URN)10.1002/ejoc.200900312 (DOI)000269103600020 ()
Available from: 2009-10-14 Created: 2009-10-14 Last updated: 2017-12-12Bibliographically approved
5. Efficient aerobic ruthenium-catalyzed oxidation of secondary alcohols by the use of a hybrid electron transfer catalyst
Open this publication in new window or tab >>Efficient aerobic ruthenium-catalyzed oxidation of secondary alcohols by the use of a hybrid electron transfer catalyst
Show others...
2010 (English)In: European Journal of Organic Chemistry, ISSN 1434-193X, E-ISSN 1099-0690, no 10, 1971-1976 p.Article in journal (Refereed) Published
Abstract [en]

Biomimetic aerobic oxidation of secondary alcohols has been performed using hybrid catalyst 1 and Shvo's catalyst 2. This combination allows mild reaction conditions and low catalytic loading, due to the efficiency of intramolecular electron transfer. By this method a wide range of different alcohols have been converted into their corresponding ketones. Oxidation of benzylic as well as aliphatic, electron-rich, electron-deficient and sterically hindered alcohols could be oxidized in excellent yield and selectivity. Oxidation of (S)-1-phenyl-ethanol showed that no racemization occurred during the course of the reaction, indicating that the hydride 2b adds to the quinone much faster than it re-adds to the ketone product. The kinetic deuterium isotope effect of the oxidation was determined by the use of 1-phenylethanol (3a) and 1-deuterio-1-phenylethanol (3a-d1) in parallel and competitive manner, which gave the same isotope effect within experimental error (k(H)/k(D) approximate to 2.8). This indicates that there is no strong coordination of the substrate to the catalyst.

Keyword
Oxidation, Alcohols, Electron transfer, Hybrid catalysts, Ruthenium
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-45863 (URN)10.1002/ejoc.201000033 (DOI)000276742400017 ()
Funder
Knut and Alice Wallenberg FoundationSwedish Research Council
Note
authorCount :5Available from: 2010-11-15 Created: 2010-11-15 Last updated: 2017-12-12Bibliographically approved

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