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Highly Selective Iridium-Catalyzed Asymmetric Hydrogenation of Trifluoromethyl Olefins: A New Route to Trifluoromethyl-Bearing Stereocenters
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Biochemistry and Organic Chemistry.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Biochemistry and Organic Chemistry.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Biochemistry and Organic Chemistry.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Physical and Analytical Chemistry.
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2009 (English)In: Advanced Synthesis and Catalysis, ISSN 1615-4150, E-ISSN 1615-4169, Vol. 351, no 3, 375-378 p.Article in journal (Refereed) Published
Abstract [en]

Fluorine-containing compounds are useful in many applications ranging from pharmaceuticals to ferroelectric crystals. We have developed a new, highly enantioselective synthetic route to trifluoromethyl-bearing stereocenters in up to 96% ee via asymmetric hydrogenation using N,P-ligated iridium catalysts. We also hydrogenated an isomeric mixture of olefins; this reaction gave the hydrogenation product highly enantioselectively (87% ee), and only the E isomer was present after the reaction had reached 56% conversion.

Place, publisher, year, edition, pages
2009. Vol. 351, no 3, 375-378 p.
Keyword [en]
asymmetric catalysis, fluorine, hydrogenation, iridium, P-N ligands
National Category
Analytical Chemistry
Research subject
Analytical Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-100634DOI: 10.1002/adsc.200800645ISI: 000264058900016OAI: oai:DiVA.org:uu-100634DiVA: diva2:210718
Available from: 2009-04-03 Created: 2009-04-03 Last updated: 2011-03-29Bibliographically approved
In thesis
1. Synthesis and Evaluation of N,P-Chelating Ligands in Asymmetric Transition-Metal-Catalyzed Reactions: Ir-Catalyzed Asymmetric Hydrogenation and Pd-Catalyzed Asymmetric Intermolecular Heck Reaction
Open this publication in new window or tab >>Synthesis and Evaluation of N,P-Chelating Ligands in Asymmetric Transition-Metal-Catalyzed Reactions: Ir-Catalyzed Asymmetric Hydrogenation and Pd-Catalyzed Asymmetric Intermolecular Heck Reaction
2009 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis describes synthesis of new chiral N,P ligands and their evaluation in two types of asymmetric transition-metal catalyzed reactions.

The first part of the thesis describes studies in iridium-catalyzed asymmetric hydrogenation. A new class of chiral N,P ligands, imidazole-phosphines, was synthesized and evaluated in the Ir-catalyzed asymmetric hydrogenation of olefins (Paper I). The new ligands proved to be highly efficient and enantioselective in the reaction. Because the substrate scope of Ir-catalyzed asymmetric hydrogenation is still limited to certain types of test substrates, new substrate classes with importance in medicinal and materials chemistry were investigated. Vinyl fluorides were efficiently hydrogenated to fluorine-containing chiral centers by the iridium catalysts with imidazole-phosphine ligands (Paper I). To obtain CF3-bearing chiral centers, we hydrogenated CF3-substituted olefins (Paper II). Ir-catalyzed asymmetric  hydrogenation was highly enantioselective for the functionalized CF3-substituted olefins and the resulting chiral products can be valuable in design of materials such as LCD screens. Ir-catalyzed asymmetric hydrogenation was also evaluated as a route to diarylmethine chiral centers (Paper III). A wide range of new chiral compounds possessing a diarylmethine chiral center was obtained.

The second part of the thesis deals with asymmetric intermolecular Heck reaction utilizing N,P ligands. The N,P ligand class of thiazole-phosphines was evaluated in the Heck reaction (Paper IV) and gave high enantioselectivity. Further, the intermolecular Heck reaction was examined using computational and experimental studies (Paper V). This study led to a better understanding of the enantioselectivity in the reaction.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2009. 74 p.
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 681
Keyword
Asymmetric hydrogenation, Heck reaction, N, P ligand, Iridium, Palladium, Asymmetric catalysis, Alkenes, Fluorine, Diarylmethine stereocenters
National Category
Chemical Sciences
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:uu:diva-108940 (URN)978-91-554-7632-8 (ISBN)
Public defence
2009-11-26, sal B41, BMC, Husargatan 3, Uppsala, 10:15 (English)
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Supervisors
Available from: 2009-11-05 Created: 2009-10-05 Last updated: 2009-11-05Bibliographically approved

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Bergquist, JonasAndersson, Pher G

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