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Highly Selective Cascade C-C Bond Formation via Palladium-Catalyzed Oxidative Carbonylation-Carbocyclization-Carbonylation-Alkynylation of Enallenes
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.
2015 (English)In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 137, no 37, 11868-11871 p.Article in journal (Refereed) Published
Abstract [en]

A highly efficient palladium-catalyzed oxidative cascade reaction of enallenes undergoing overall four C-C bond formations has been developed. The insertion cascade proceeds via carbonylation carbocyclization carbonylation alkynylation involving sequential insertion of carbon monoxide, olefin, and carbon monoxide. Furthermore, different types of terminal alkynes and functionalized enallenes have been investigated and found to undergo the cascade reaction under mild reaction conditions.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2015. Vol. 137, no 37, 11868-11871 p.
National Category
Chemical Sciences
Identifiers
URN: urn:nbn:se:su:diva-122320DOI: 10.1021/jacs.5b06828ISI: 000361930000004OAI: oai:DiVA.org:su-122320DiVA: diva2:876125
Funder
EU, European Research CouncilBerzelii Centre EXSELENTKnut and Alice Wallenberg Foundation
Available from: 2015-12-02 Created: 2015-10-29 Last updated: 2017-04-06Bibliographically approved
In thesis
1. Catalytic Stereoselective Formation of C–O, C–C and C–B Bonds: A Voyage from Asymmetric Reactions Enabled by Lipases to Stereoselective Palladium-Catalyzed Oxidative Transformations of Enallenes
Open this publication in new window or tab >>Catalytic Stereoselective Formation of C–O, C–C and C–B Bonds: A Voyage from Asymmetric Reactions Enabled by Lipases to Stereoselective Palladium-Catalyzed Oxidative Transformations of Enallenes
2017 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis has been focused on enzymatic kinetic resolutions and stereoselective oxidative transformations of enallenes catalyzed by PdII.

In the first part of the thesis, a detailed discussion on Candida antarctica lipase B (CALB)-catalyzed kinetic resolution (KR) of δ-functionalized alkan-2-acetates is shown. We gained a deeper insight into the mechanism of enzyme-substrate recognition. Changing from an anhydrous solvent to water or a water-containing organic solvent enhanced the enantioselectivity. The effect of –OH was also confirmed by a lipase mutant suggesting that the water molecule mentioned above can be partly mimicked.

In the second part of the thesis, we developed an efficient KR for allenic alcohols. On this basis, a novel synthesis of optically pure 2-substituted 2,3-dihydrofurans from allenic alcohols via a Ru-catalyzed cycloisomerization was reported. The developed protocol enabled us to assemble an optically pure precursor for total synthesis with three chiral centers from readily available allenol in 2 days.

In the third part, we reported a class of reactions involving C–H cleavage under mild conditions: PdII-catalyzed oxidative transformations of enallenes. These reactions are particularly attractive since a number of meticulous structures have been achieved from readily accessible starting materials. The directing effect of an unsaturated hydrocarbon was found to be key for these transformations.

In the final part, we developed the carbonylative insertion reaction discussed in the third part of the thesis into an asymmetric version. By using this methodology, a number of cyclopentenone compounds were obtained in good to excellent enantioselectivity.

Place, publisher, year, edition, pages
Stockholm: Department of Organic Chemistry, Stockholm University, 2017. 76 p.
Keyword
Synthesis, Enzymatic kinetic resolution, Palladium, Allenes, Oxidative Transformations, Ruthenium
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-141519 (URN)978-91-7649-823-1 (ISBN)978-91-7649-824-8 (ISBN)
Public defence
2017-05-17, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 13:00 (English)
Opponent
Supervisors
Available from: 2017-04-24 Created: 2017-04-05 Last updated: 2017-05-23Bibliographically approved

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Zhu, CanYang, BinBäckvall, Jan-E.
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