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A New Highly Asymmetric Chelation-Controlled Heck Arylation
Uppsala University, Disciplinary Domain of Medicine and Pharmacy, Faculty of Pharmacy, Department of Medicinal Chemistry.
Uppsala University, Disciplinary Domain of Medicine and Pharmacy, Faculty of Pharmacy, Department of Medicinal Chemistry, Organic Pharmaceutical Chemistry.
2003 (English)In: Journal of the American Chemical Society, Vol. 125, no 12, 3430-3431 p.Article in journal (Refereed) Published
Place, publisher, year, edition, pages
2003. Vol. 125, no 12, 3430-3431 p.
National Category
Medical and Health Sciences
Identifiers
URN: urn:nbn:se:uu:diva-90945OAI: oai:DiVA.org:uu-90945DiVA: diva2:163475
Available from: 2003-10-27 Created: 2003-10-27 Last updated: 2013-07-04Bibliographically approved
In thesis
1. Selectivity in Palladium- and Enzyme-Catalyzed Reactions: Focusing on Enhancement of Reactivity
Open this publication in new window or tab >>Selectivity in Palladium- and Enzyme-Catalyzed Reactions: Focusing on Enhancement of Reactivity
2003 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Catalysis has a profound impact on all living species on the earth. Nature’s catalysts, the enzymes, have the ability to selectively promote a specific bio-chemical transformation, given the required substrate. As well as being highly selective, enzymes enhance the speed of these reactions, helping them to run at temperatures much lower than normally required, i.e. at body temperature. In comparison, reactions used in the production of new materials such as polymers, medicines, fragrances, petrochemicals, etc. are often catalyzed by transition metals. This thesis describes how the selectivity and activity of these catalysts can be influenced via two conceptually different methods: chelation control and microwave heating. The thesis primarily focuses on regio- and stereochemical aspects of the palladium-catalyzed arylation of olefins, i.e. the Heck reaction. Reaction rate enhancement of both palladium and enzyme (polymerase chain reaction [PCR]) catalysis by microwave heating is also discussed.

Novel chelation-controlled palladium-catalyzed multi- and asymmetric arylations of vinyl ethers were performed, resulting in tetra-substituted olefins as well as chiral quaternary carbon centers with excellent optical purity. In addition, a new synthetic route to diarylated ethanals, relying on a double chelation-controlled regioselective arylation followed by hydrolysis, has been discovered. High temperature conditions, using microwave heating, substantially reduce the reaction time for ligand-controlled asymmetric Heck arylations, while retaining levels of enantioselectivity in most cases. In addition, a potentially useful fast synthetic protocol for the employment of aryl boronic acids in oxidative Heck arylation was developed. Finally, microwave-assisted PCR was described for the first time; this method allows reductions in the run time of 50%.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2003. 76 p.
Series
Comprehensive Summaries of Uppsala Dissertations from the Faculty of Pharmacy, ISSN 0282-7484 ; 299
Keyword
Pharmaceutical chemistry, Palladium, Heck, PCR, Microwaves, Farmaceutisk kemi
National Category
Medicinal Chemistry
Identifiers
urn:nbn:se:uu:diva-3625 (URN)91-554-5765-7 (ISBN)
Public defence
2003-11-21, B41, BMC, Uppsala, 13:15
Opponent
Supervisors
Available from: 2003-10-27 Created: 2003-10-27Bibliographically approved

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