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Studies of Biomimtic Oxidations and Racemizations
Stockholm University, Faculty of Science, Department of Organic Chemistry.
2004 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis deals with studies of ruthenium-catalyzed hydrogen transfer reactions for oxidations and racemization.

Through optimisation of the substrate-selective redox catalyst, the electron and proton transfer mediator (a benzoquinone derivative), and the oxygen-activating metal macrocycle a highly efficient biomimetic oxidation of secondary alcohols was obtained. Several alcohols were subjected to the new oxidation protocol and the corresponding ketones were isolated in high yield.

The deactivation of the oxygen-activating metal macrocycle retarded the aerobic oxidation of primary alcohols. Encapsulation of the metal macrocycle into zeolite, described in chapter 3, proved to be an efficient method to solve this problem and comparable conversion of alcohols was achieved. The immobilization of the oxygen-activating porphyrin to a surface can be an alternative approach to solve the deactivation problem. Therefore as the first step towards studies of immobilized porphyrins on a metal surface (of gold or silver), S-thioacetyl derivatized porphyrins were synthesized; two alternative syntheses are described in chapter 4.

A new and effecient ruthenium-catalyzed racemization protocol was established by proper ligand tuning. The racemization of the enantiomerically pure alcohols was increased significantly; this work is reported in chapter 5.

Place, publisher, year, edition, pages
Stockholm: Institutionen för organisk kemi , 2004. , 52 p.
Keyword [en]
oxidation of alcohols, ruthenium, porphyrin, racemization
National Category
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-71ISBN: 91-7265-819-3 (print)OAI: oai:DiVA.org:su-71DiVA: diva2:197629
Public defence
2004-04-01, Magnélisalen, Arrheniuslaboratoriet, Svante Arrhenius väg 12 A, Stockholm, 14:00
Opponent
Supervisors
Available from: 2004-03-11 Created: 2004-03-11 Last updated: 2013-08-15Bibliographically approved
List of papers
1. Efficient Ruthenium-Catalyzed Aerobic Oxidation of Alcohols Using a Biomimetic Coupled Catalytic System
Open this publication in new window or tab >>Efficient Ruthenium-Catalyzed Aerobic Oxidation of Alcohols Using a Biomimetic Coupled Catalytic System
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2002 In: Journal of Organic Chemistry, ISSN 0022-3263, Vol. 67, no 5, 1657-1662 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-24476 (URN)
Note
Part of urn:nbn:se:su:diva-71Available from: 2004-03-11 Created: 2004-03-11Bibliographically approved
2. Ruthenium-Catalyzed Aerobic Oxidation of Alcohols on Zeolite-Encapsulated Cobalt Salophen Catalyst
Open this publication in new window or tab >>Ruthenium-Catalyzed Aerobic Oxidation of Alcohols on Zeolite-Encapsulated Cobalt Salophen Catalyst
2002 In: Topics in catalysis, ISSN 1022-5528, Vol. 19, no 1, 119-124 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-24477 (URN)
Note
Part of urn:nbn:se:su:diva-71Available from: 2004-03-11 Created: 2004-03-11Bibliographically approved
3. Synthesis os S-Thioacetate Functionalized Cobalt(II) Porphyrins and Heterogenization on gold Surface
Open this publication in new window or tab >>Synthesis os S-Thioacetate Functionalized Cobalt(II) Porphyrins and Heterogenization on gold Surface
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2006 (English)In: European Journal of Organic Chemistry, ISSN 1434-193X, E-ISSN 1099-0690, no 5, 1193-1199 p.Article in journal (Refereed) Published
Abstract [en]

Cobalt tetraarylporphyrins 1-Co and 2-Co with thioacetate-functionalized carbon chains on the aryl groups were synthesized. The cobalt porphyrin 2-Co was immobilized on a gold surface after deprotection of the S-acetyl group. The immobilized porphyrin was studied by X-ray Photoelectron Spectroscopy (XPS) and the results suggest that a complete monolayer of porphyrins is formed.

Place, publisher, year, edition, pages
Wiley-VCH Verlagsgesellschaft, 2006
Keyword
functionalized porphyrin, immobilization, gold surface, monolayers, photoelectron spectroscopy
National Category
Chemical Sciences
Identifiers
urn:nbn:se:su:diva-24478 (URN)10.1002/ejoc.200500656 (DOI)
Note

Part of urn:nbn:se:su:diva-71

Available from: 2004-03-11 Created: 2004-03-11 Last updated: 2013-08-14Bibliographically approved
4. New Efficient Ruthenium Catalysts for Racemization of Alcohols at Room Temperature
Open this publication in new window or tab >>New Efficient Ruthenium Catalysts for Racemization of Alcohols at Room Temperature
2004 (English)In: Tetrahedron Letters, ISSN 0040-4039, E-ISSN 1873-3581, Vol. 45, no 36, 6799-6802 p.Article in journal (Refereed) Published
Abstract [en]

5-Pentaphenylcyclopentadienyl)RuCl(CO)2 was found to catalyze efficiently the racemization of chiral alcohols such as (S)-1-phenylethanol, (S)-1-phenylpropan-2-ol, (S)-4-phenylbutan-2-ol and (S)-4-methoxy-1-phenylethanol at room temperature in the presence of a base. The catalytic activity of three other Ru(II) complexes was also investigated. The effects of halide and solvent were studied as well.

National Category
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-24330 (URN)10.1016/j.tetlet.2004.07.013 (DOI)
Available from: 2007-05-30 Created: 2007-05-23 Last updated: 2013-08-15Bibliographically approved

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