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Regioselective Iridium-Catalyzed Asymmetric Monohydrogenation of 1,4-Dienes
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: 72017 (English)In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 139, no 41, p. 14470-14475Article in journal (Refereed) Published
Abstract [en]

A highly efficient regio- and enantioselective monohydrogenation of 1,4-dienes has been realized using an iridium catalyst with a chiral N,P-ligand under mild conditions. The substrate scope was studied and included both unfunctionalized as well as functionalized substituents on the meta- or para-position. Substrates having substituents with functionalities such as silyl protected alcohols or ketals were monohydrogenated in high regioselectivity and high enantiomeric excess (up to 98% ee).

Place, publisher, year, edition, pages
2017. Vol. 139, no 41, p. 14470-14475
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-149001DOI: 10.1021/jacs.7b06829ISI: 000413503300025PubMedID: 28930455OAI: oai:DiVA.org:su-149001DiVA, id: diva2:1160385
Funder
Swedish Research CouncilStiftelsen Olle Engkvist ByggmästareSwedish Energy AgencyAvailable from: 2017-11-27 Created: 2017-11-27 Last updated: 2018-05-09Bibliographically 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. p. 52
Keywords
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)
Opponent
Supervisors
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: 2018-03-22Bibliographically approved
2. Development of Asymmetric Iridium Catalysed Hydrogenation Reactions
Open this publication in new window or tab >>Development of Asymmetric Iridium Catalysed Hydrogenation Reactions
2018 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The focus of the work presented in this thesis is the development of iridium-catalysed asymmetric hydrogenation reactions.

The first part of this thesis covers the development of dynamic kinetic resolution in asymmetric hydrogenation of chiral, racemic secondary allylic alcohols, which are converted to chiral saturated alcohols with high dr and ee. In this study, a wide range of substrates was successfully hydrogenated to give good results, with up to 95:5 dr and 99% ee. Moreover, a number of different allylic alcohol derivatives were also investigated and found to undergo the DKR of hydrogenation with good results.

The second part of this thesis is directed towards the development of regioselective asymmetric mono-hydrogenation of 1,4- and 1,5-disubstituted 1,4-cyclohexadienes. Under optimized hydrogenation conditions, high yield of regioselective mono-hydrogenated products and excellent enantioselectivity were observed in most cases. The usefulness of the reaction was demonstrated in the preparation of important chiral α,β-unsaturated ketones in good yield and excellent ee of up to 96%. Our novel method provides a general route to this important class of compounds.

The third part concerns the development of asymmetric hydrogenation of β-hydroxy silanes. It was observed that under hydrogenation conditions, β-hydroxy silanes undergo Peterson olefination to form terminal olefins which are then hydrogenated using an Ir catalyst. A new class of Ir-N,P catalysts were prepared and provided high yield with excellent ee in up to 99%. In addition, the reaction was highly chemoselective and could be tuned to hydrogenate either an olefin or a β-hydroxy silane depending on the choice of catalyst and reaction conditions.

The final part describes the asymmetric hydrogenation of enamides. A variety of oxazolidinone-enamides were prepared and evaluated in this reaction. High yields, (up to 99%) and excellent ee, (up to 99%) were obtained.

Place, publisher, year, edition, pages
Stockholm: Department of Organic Chemistry, Stockholm University, 2018. p. 70
Keywords
Asymmetric hydrogenation, Iridium catalyst, Peterson olefination, Dynamic Kinetic Resolution
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-156339 (URN)978-91-7797-300-3 (ISBN)978-91-7797-301-0 (ISBN)
Public defence
2018-06-26, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 10:00 (English)
Opponent
Supervisors
Note

At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 1: Accepted. Paper 3: Manuscript. Paper 4: Manuscript.

Available from: 2018-06-01 Created: 2018-05-09 Last updated: 2018-06-04Bibliographically approved

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