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Dynamic Kinetic Resolution of Homoallylic Alcohols: Application to the Synthesis of Enantiomerically Pure 5,6-Dihydropyran-2-ones and delta-Lactones
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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2013 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 19, no 41, 13859-13864 p.Article in journal (Refereed) Published
Abstract [en]

Dynamic kinetic resolution of various homoallylic alcohols with the use of Candida antarctica lipaseB and ruthenium catalyst 2 afforded homoallylic acetates in high yields and with high enantioselectivity. These enantiopure acetates were further transformed into homoallylic acrylates after hydrolysis of the ester function and subsequent DMAP-catalyzed esterification with acryloyl chloride. After ring-closing metathesis 5,6-dihydropyran-2-ones were obtained in good yields. Selective hydrogenation of the carboncarbon double bond afforded the corresponding -lactones without loss of chiral information.

Place, publisher, year, edition, pages
2013. Vol. 19, no 41, 13859-13864 p.
Keyword [en]
dynamic kinetic resolution, homoallylic alcohols, lactones, racemization, ruthenium catalysis
National Category
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-95745DOI: 10.1002/chem.201301980ISI: 000325135800031OAI: oai:DiVA.org:su-95745DiVA: diva2:662291
Funder
Swedish Research CouncilKnut and Alice Wallenberg Foundation
Note

AuthorCount:5;

Available from: 2013-11-06 Created: 2013-11-04 Last updated: 2017-12-06Bibliographically approved
In thesis
1. Ruthenium-Catalyzed Hydrogen Transfer Reactions: Mechanistic Studies and Chemoenzymatic Dynamic Kinetic Resolutions
Open this publication in new window or tab >>Ruthenium-Catalyzed Hydrogen Transfer Reactions: Mechanistic Studies and Chemoenzymatic Dynamic Kinetic Resolutions
2013 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The main focus of this thesis lies on transition metal-catalyzed hydrogen transfer reactions. In the first part of the thesis, the mechanism for racemization of sec-alcohols with a ruthenium complex, Ru(CO)2Cl(η5-C5Ph5) was studied.

The reaction between 5-hexen-2-ol and Ru(CO)2(Ot-Bu)(η5-C5Ph5) was studied with the aim to elucidate the origin of the slow racemization observed for this sec-alcohol. Two diastereomers of an alkoxycarbonyl complex, which has the double bond coordinated to ruthenium, were characterized by NMR and in situ FT-IR spectroscopy. The observed inhibition of the rate of racemization for substrates with double bonds provided further confirmation of the importance of a free coordination site on ruthenium for β-hydride elimination. Furthermore, we observed that CO exchange, monitored by 13C NMR using 13CO, occurs with both the precatalyst, Ru(CO)2Cl(η5-C5Ph5), and the active catalytic intermediate, Ru(CO)2(Ot-Bu)(η5-C5Ph5). It was also found that added CO has an inhibitory effect on the rate of racemization of (S)-1-phenylethanol. Both these observations provide strong support for reversible CO dissociation as a key step in the racemization mechanism.

In the second part of this thesis, Ru(CO)2Cl(η5-C5Ph5) was combined with an enzymatic resolution catalyzed by a lipase, leading to several efficient dynamic kinetic resolutions (DKR). DKR of exocyclic allylic alcohols afforded the corresponding acetates in high yields and with excellent enantiomeric excess (ee). The products were utilized as synthetic precursors for α-substituted ketones and lactones. DKR of a wide range of homoallylic alcohols afforded the products in good to high yields and with high ee. The homoallylic acetates were transformed into 5,6-dihydropyran-2-ones in a short reaction sequence. Furthermore, DKR of a wide range of aromatic β-chloroalcohols afforded the products in high yields and with excellent ee. The β-chloro acetates were further transformed into chiral epoxides.

Place, publisher, year, edition, pages
Stockholm: Department of Organic Chemistry, Stockholm University, 2013. 84 p.
Keyword
Hydrogen transfer, ruthenium catalysis, kinetic resolution, dynamic kinetic resolution, racemization, asymmetric synthesis
National Category
Natural Sciences
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-89263 (URN)978-91-7447-706-1 (ISBN)
Public defence
2013-05-24, 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 2: Manuscript. Paper 5: Mansucript.

Available from: 2013-04-18 Created: 2013-04-17 Last updated: 2013-11-06Bibliographically approved

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