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Enantio- and Regioselective Ir-Catalyzed Hydrogenation of Di- and Trisubstituted Cycloalkenes
Stockholm University, Faculty of Science, Department of Organic Chemistry.
Stockholm University, Faculty of Science, Department of Organic Chemistry.
Stockholm University, Faculty of Science, Department of Organic Chemistry.
Stockholm University, Faculty of Science, Department of Organic Chemistry.
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Number of Authors: 8
2016 (English)In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 138, no 36, 11930-11935 p.Article in journal (Refereed) Published
Abstract [en]

A number of cyclic olefins Were prepared and evaluated for the asymmetric hydrogenation reaction using novel N,P-ligated iridium imidazote-based Catalysts (Crabtree type). The diversity of these cyclic olefins spanned those having little functionality to others bearing strongly coordinating substituents and heterocycles. Excellent enantioselectivities were observed both for substrates having little functionality (up to >99% ee) and for substrates possessing functional groups several carbons away from the olefin. Substrates having functionalities such as carboxyl groups, alcohols, or heterocycles in the vicinity of the C=C bond were hydrogenated in high enantiomeric excess (up to >99% ee). The hydrogenation was also found to be regioselective, and by controlling the reaction conditions, selective hydrogenation of one of two trisubstituted olefins can be achieved: Furthermore, trisubstituted olefins can be selectively hydrogenated in the presence of tetrasubstituted olefins.

Place, publisher, year, edition, pages
2016. Vol. 138, no 36, 11930-11935 p.
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-135188DOI: 10.1021/jacs.6b07291ISI: 000383410700067PubMedID: 27548029OAI: oai:DiVA.org:su-135188DiVA: diva2:1048614
Available from: 2016-11-21 Created: 2016-11-01 Last updated: 2017-03-28Bibliographically approved
In thesis
1. Iridium Catalysed Asymmetric Hydrogenation of Olefins and Dynamic Kinetic Resolution in the Asymmetric Hydrogenation of Allylic Alcohols
Open this publication in new window or tab >>Iridium Catalysed Asymmetric Hydrogenation of Olefins and Dynamic Kinetic Resolution in the Asymmetric Hydrogenation of Allylic Alcohols
2017 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The work described in this thesis is focused on exploring the efficacy of iridium-catalysed asymmetric hydrogenation of precursors to chiral alcohols and chiral cyclohexanes. A range of allylic alcohols including γ,γ-dialkyl allylic alcohols and (Z)-allylic alcohols were prepared and evaluated in the asymmetric hydrogenation using iridium catalysts resulting in chiral alcohols in high yields and excellent enantioselectivity. This methodology was applied in the formal synthesis of Aliskiren, an efficient renin inhibitor drug, using the asymmetric hydrogenation of an allylic alcohol as a key-step. Another project concerned the dynamic kinetic resolution of racemic secondary allylic alcohols using Ir-N,P catalysts under hydrogenation conditions. A range of secondary allylic alcohols and protected alcohols were evaluated in the asymmetric hydrogenation via dynamic kinetic resolution using Ir-N,P catalysts. The corresponding chiral saturated alcohols were formed in good yield with excellent diastereoselectivites (up to 95/5) and enantioselectivities (>99% ee). The last part of this thesis is directed towards the development of highly regio- and enantioselective asymmetric hydrogenation of 1,4-cyclohexadienes and its application in the preparation of useful chiral cyclohexenone intermediates. Non-functionalised, functionalised and heterocycle-containing cyclohexadienes were evaluated. Good yield of regioselectively mono-hydrogenated silyl protected enol ethers were obtained in most cases with excellent enantioselectivity. 

Place, publisher, year, edition, pages
Stockholm: Department of Organic Chemistry, Stockholm University, 2017. 52 p.
Keyword
Iridium catalyst, asymmetric hydrogenation, dynamic kinetic resolution, allylic alcohol
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-140923 (URN)978-91-7649-744-9 (ISBN)978-91-7649-745-6 (ISBN)
Public defence
2017-05-02, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius Väg 16 B, Stockholm, 10:00 (English)
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Note

At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 3: Manuscript. Paper 5: Manuscript.

Available from: 2017-04-07 Created: 2017-03-23 Last updated: 2017-04-03Bibliographically approved

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