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Iridium phosphite-oxazoline catalysts for the highly enantioselective hydrogenation of terminal alkenes
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Biochemistry and Organic Chemistry, Organic Chemistry I.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Biochemistry and Organic Chemistry.
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2009 (English)In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 131, no 34, 12344-12353 p.Article in journal (Refereed) Published
Abstract [en]

A modular library of readily available phosphite-oxazoline ligands (L1-L16a-f) has been successfully applied for the first time in the Ir-catalyzed asymmetric hydrogenation of a broad range of highly unfunctionalized 1,1,-disubstituted terminal alkenes. Enantioselectivities up to >99% and full conversions were obtained in several 1,1-disubstituted alkenes, including substrate classes that have never been asymmetrically hydrogenated before (i.e., 1,1-heteoraryl-alkyl, 1,1-diaryl, trifluoromethyl, etc.). The results indicated that these catalytic systems have high tolerance to the steric and electronic requirements of the substrate and also to the presence of a neighboring polar group. The asymmetric hydrogenations were also performed using propylene carbonate as solvent, which allowed the Ir catalyst to be reused and maintained the excellent enantioselectivities.

Place, publisher, year, edition, pages
2009. Vol. 131, no 34, 12344-12353 p.
National Category
Chemical Sciences
URN: urn:nbn:se:uu:diva-121863DOI: 10.1021/ja904152rISI: 000269379600068PubMedID: 19658416OAI: oai:DiVA.org:uu-121863DiVA: diva2:306888
Available from: 2010-03-31 Created: 2010-03-31 Last updated: 2012-11-12Bibliographically approved
In thesis
1. Transition Metal Catalysis for Selective Synthesis and Sustainable Chemistry
Open this publication in new window or tab >>Transition Metal Catalysis for Selective Synthesis and Sustainable Chemistry
2012 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis discusses the preparation and use of transition-metal catalysts for selective organic chemical reactions. Specifically, two different matters have been studied; the asymmetric hydrogenation of carbon-carbon double bonds using N,P-ligated iridium catalysts and the metal-catalyzed transfer of small molecules from biomass to synthetic intermediates.

In the first part of this thesis, chiral N,P-ligands were synthesized and evaluated in iridium catalysts for the asymmetric hydrogenation of non- and weakly functionalized alkenes (Papers I & II). The new catalysts were prepared via chiral-pool strategies and exhibited superior properties for the reduction of certain types of alkenes. In particular, some of the catalysts showed excellent activity and selectivity in the enantioselective reduction of terminal alkenes, and the preparation of a modular catalyst library allowed the asymmetric hydrogenation of a wide range of 1,1-disubstituted alkenes with unprecedented efficiency and enantioselectivity (Paper III). Methods for the selective preparation of chiral hetero- and carbocyclic fragments using iridium-catalyzed asymmetric hydrogenation as an enantiodetermining key step were also developed. A range of elusive chiral building blocks that have applications in pharmaceutical and natural-product chemistry could thus be conveniently prepared (Papers IV & V).

The second part of this thesis deals with the catalytic decomposition of polysaccharides into sugar alcohols and the incorporation of their decomposition products into alkene substrates. Iridium-catalyzed dehydrogenative decarbonylation was found to decompose polyols into CO:H2 mixtures that could be used immediately in the ex situ low-pressure hydroformylation of styrene (Paper VI). The net process was thus the hydroformylation of alkenes with biomass-derived synthesis gas.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2012. 125 p.
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 984
Catalysis, Transition metals, Asymmetric catalysis, Hydrogenation, Sustainable chemistry
National Category
Organic Chemistry
Research subject
Chemistry with specialization in Organic Chemistry
urn:nbn:se:uu:diva-182900 (URN)978-91-554-8507-8 (ISBN)
Public defence
2012-11-30, B42, BMC, Husargatan 3, Uppsala, 10:00 (English)
Available from: 2012-11-09 Created: 2012-10-18 Last updated: 2013-01-23

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