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Ir-Catalyzed Asymmetric and Regioselective Hydrogenation of Cyclic Allylsilanes and Generation of Quaternary Stereocenters via the Hosomi-Sakurai Allylation
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 Materials and Environmental Chemistry (MMK).
Stockholm University, Faculty of Science, Department of Organic Chemistry.
2018 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 24, no 7, p. 1681-1685Article in journal (Refereed) Published
Abstract [en]

A number of cyclic dienes containing the allylsilane moiety were prepared via Birch reduction and subjected to iridium-catalyzed regioselective and asymmetric hydrogenation, which provided chiral allylsilanes in high conversion and enantiomeric excess (up to 99 % ee). The compounds were successively used in the Hosomi-Sakurai allylation with various aldehydes employing TiCl4 as Lewis acid, providing adducts with two additional stereogenic centers in excellent diastereoselectivity.

Place, publisher, year, edition, pages
2018. Vol. 24, no 7, p. 1681-1685
Keyword [en]
allylation, asymmetric reactions, hydrogenation, iridium, regioselectivity
National Category
Chemical Sciences
Research subject
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-150597DOI: 10.1002/chem.201704684ISI: 000423804800026OAI: oai:DiVA.org:su-150597DiVA, id: diva2:1169496
Funder
Stiftelsen Olle Engkvist Byggmästare
Available from: 2017-12-27 Created: 2017-12-27 Last updated: 2018-03-22Bibliographically approved
In thesis
1. The Use of N,P-Iridium and N,P-Palladium Complexes in Asymmetric Synthesis
Open this publication in new window or tab >>The Use of N,P-Iridium and N,P-Palladium Complexes in Asymmetric Synthesis
2018 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The work presented in this thesis concerns asymmetric catalysis using chiral N,P-ligands and iridium or palladium transition metals. The first part  (Chapters 2 and 3) highlights the N,P-iridium catalyzed asymmetric hydrogenation of 1,4-cyclohexadienes having functionalized or unfunctionalized substituents, including allylsilane side chains. A series of N,P-iridium catalysts were synthesized and screened on a number of cyclohexadienes. The developed N,P-iridium catalysts have provided excellent chemo-, regio- and enantioselectivity for most of the products obtained. For substrates having an allylsilane sidechain, the chiral cyclic allylsilane products were used to induce stereocontrol in a subsequent Hosomi-Sakurai reaction using TiCl4 as Lewis acid and aldehydes as electrophiles. The corresponding homoallylic alcohols were obtained in good to excellent diastereoselectivity. 

The second part (Chapter 4) describes the N,P-iridium catalyzed asymmetric hydrogenation of various vinyl fluorides. A number of tri- and tetrasubstituted vinyl fluorides were synthesized and evaluated for the asymmetric hydrogenation. The corresponding saturated chiral fluoro compounds were obtained in very high enantioselectivity (up to 99% ee). The defluorination, usually known to occur under the catalytic hydrogenation conditions, were not observed for the majority of the substrates. 

Finally, Chapter 5 describes the application of N,P-ligands in the asymmetric cycloisomerization of 1,6-enynes using a palladium precatalyst. The enantioselectivities for the products were found to depend both on the substrate as well as the hydrogen source. These developed catalytic reactions provide attractive methods to create multiple stereogenic centers in a molecule in relatively few steps from readily available starting materials.

Place, publisher, year, edition, pages
Stockholm: Department of Organic Chemistry, Stockholm University, 2018. p. 66
Keyword
Iridium, Asymmetric Hydrogenation, Palladium, Asymmetric Cycloisomerization and Hosomi-Sakurai Allylation
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-150602 (URN)978-91-7797-061-3 (ISBN)978-91-7797-062-0 (ISBN)
Public defence
2018-01-31, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 10:00 (English)
Opponent
Supervisors
Note

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

Available from: 2018-01-08 Created: 2017-12-27 Last updated: 2018-01-11Bibliographically approved

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