Change search
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf
Enantioselective Route to Ketones and Lactones from Exocyclic Allylic Alcohols via Metal and Enzyme Catalysis
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.
2012 (English)In: Organic Letters, ISSN 1523-7060, E-ISSN 1523-7052, Vol. 14, no 19, 5094-5097 p.Article in journal (Refereed) Published
Abstract [en]

A general and efficient route for the synthesis of enantiomerically pure a-substituted ketones and the corresponding lactones has been developed. Ruthenium- and enzyme-catalyzed dynamic kinetic resolution (DKR) with a subsequent Cu-catalyzed alpha-allylic substitution are the key steps of the route. The a-substituted ketones were obtained in high yields and with excellent enantiomeric excess. The methodology was applied to the synthesis of a naturally occurring caprolactone, (R)-10-methyl-6-undecanolide, via a subsequent Baeyer-Villiger oxidation.

Place, publisher, year, edition, pages
2012. Vol. 14, no 19, 5094-5097 p.
National Category
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-82136DOI: 10.1021/ol302358jISI: 000309438400030OAI: oai:DiVA.org:su-82136DiVA: diva2:566666
Funder
Swedish Research CouncilKnut and Alice Wallenberg Foundation
Note

AuthorCount:4;

Available from: 2012-11-09 Created: 2012-11-08 Last updated: 2017-12-07Bibliographically 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

Open Access in DiVA

No full text

Other links

Publisher's full text

Search in DiVA

By author/editor
Warner, Madeleine C.Nagendiran, AnujaBäckvall, Jan-E.
By organisation
Department of Organic Chemistry
In the same journal
Organic Letters
Organic Chemistry

Search outside of DiVA

GoogleGoogle Scholar

doi
urn-nbn

Altmetric score

doi
urn-nbn
Total: 48 hits
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf