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Cross-metathesis versus palladium-catalyzed C-H activation acetoxy ester functionalization of unsaturated fatty acid methyl esters

  • Two synthetic approaches to functionalize plant oil derived platform chemicals were investigated. For this purpose, methyl 10-undecenoate, which can be obtained by pyrolysis of castor oil, was used in olefin cross-metathesis under neat conditions forming an unsaturated a,?-acetoxy ester. A catalyst screening with 11 different ruthenium-based metathesis catalysts was performed, revealing that well-suited catalysts allow for full conversion and very good cross-metathesis selectivity at a loading of only 0.5?mol%. An alternative possibility to the aforementioned synthetic method is a palladium-catalyzed reaction of methyl 10-undecenoate with acetic acid in the presence of dimethyl sulfoxide. Here, the formation of linear and branched unsaturated acetoxy esters as well as a ketone was observed. The conversion as well as the selectivity of this procedure was studied under different reaction conditions and compared to the cross-metathesis results. Based on the successful functionalization of methyl 10-undecenoate, methyl oleate wasTwo synthetic approaches to functionalize plant oil derived platform chemicals were investigated. For this purpose, methyl 10-undecenoate, which can be obtained by pyrolysis of castor oil, was used in olefin cross-metathesis under neat conditions forming an unsaturated a,?-acetoxy ester. A catalyst screening with 11 different ruthenium-based metathesis catalysts was performed, revealing that well-suited catalysts allow for full conversion and very good cross-metathesis selectivity at a loading of only 0.5?mol%. An alternative possibility to the aforementioned synthetic method is a palladium-catalyzed reaction of methyl 10-undecenoate with acetic acid in the presence of dimethyl sulfoxide. Here, the formation of linear and branched unsaturated acetoxy esters as well as a ketone was observed. The conversion as well as the selectivity of this procedure was studied under different reaction conditions and compared to the cross-metathesis results. Based on the successful functionalization of methyl 10-undecenoate, methyl oleate was investigated in this palladium-catalyzed C?H activation reaction. Due to the lower reactivity of the internal double bond the desired acetoxy ester was only obtained in moderate conversion in this case. In summary, this study clearly shows that palladium-catalyzed functionalization of unsaturated fatty compounds via C?H activation is an attractive alternative to the well-established olefin cross-metathesis procedure.show moreshow less

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Metadaten
Author:Marc von Czapiewski, Oliver Kreye, Hatice Mutlu, Michael A. R. Meier
DOI:https://doi.org/10.1002/ejlt.201200196
ISSN:1438-7697 (print)
Parent Title (English):European journal of lipid science and technology
Publisher:Wiley-Blackwell
Place of publication:Hoboken
Document Type:Article
Language:English
Year of first Publication:2013
Year of Completion:2013
Release Date:2017/03/26
Tag:-Acetoxy esters; C?H oxidation; Cross-metathesis; Fatty acids; Pd catalysis; a
Volume:115
Issue:1
Pagenumber:10
First Page:76
Last Page:85
Organizational units:Mathematisch-Naturwissenschaftliche Fakultät / Institut für Chemie
Peer Review:Referiert