Promotion of selective pathways in isomerizing functionalization of plant oils by rigid framework substituents

Handle URI:
http://hdl.handle.net/10754/563800
Title:
Promotion of selective pathways in isomerizing functionalization of plant oils by rigid framework substituents
Authors:
Christl, Josefine T.; Roesle, Philipp; Stempfle, Florian; Müller, Gerhard J.; Caporaso, Lucia; Cavallo, Luigi ( 0000-0002-1398-338X ) ; Mecking, Stefan
Abstract:
The 1,2-(CH2P(1-adamantyl)2)2C6H4 (dadpx) coordinated palladium complex [(dadpx)Pd(OTf)2] (1) is a catalyst precursor for the isomerizing methoxycarbonylation of the internal double bond of methyl oleate, with an unprecedented selectivity (96%) for the linear diester 1,19-dimethyl nonadecanedioate. Rapid formation of the catalytically active solvent-coordinated hydride species [(dadpx)PdH(MeOH)]+ (3-MeOH) is evidenced by NMR spectroscopy, and further isolation and X-ray crystal structure analysis of [(dadpx)PdH(PPh3)]+ (3-PPh3). DFT calculations of key steps of the catalytic cycle unravel methanolysis as the decisive step for enhanced selectivity and the influence of the rigid adamantyl framework on this step by destabilization of transition states of unselective pathways.
KAUST Department:
Physical Sciences and Engineering (PSE) Division; Chemical Science Program; KAUST Catalysis Center (KCC)
Publisher:
Wiley-Blackwell
Journal:
ChemSusChem
Issue Date:
14-Oct-2014
DOI:
10.1002/cssc.201402441
Type:
Article
ISSN:
18645631
Sponsors:
Financing by the Stiftung Baden-Wurttemberg (Programm Umwelttechnologieforschung, U14) is acknowledged. P.R. gratefully acknowledges support from the Carl-Zeiss-Foundation by a graduate fellowship. Donation of high oleic sunflower oil methyl ester by Dako AG is acknowledged.
Is Supplemented By:
Christl, J. T., Roesle, P., Stempfle, F., Müller, G., Caporaso, L., Cavallo, L., & Mecking, S. (2014). CCDC 992440: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc129q69; DOI:10.5517/cc129q69; HANDLE:http://hdl.handle.net/10754/624304
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; Chemical Science Program; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorChristl, Josefine T.en
dc.contributor.authorRoesle, Philippen
dc.contributor.authorStempfle, Florianen
dc.contributor.authorMüller, Gerhard J.en
dc.contributor.authorCaporaso, Luciaen
dc.contributor.authorCavallo, Luigien
dc.contributor.authorMecking, Stefanen
dc.date.accessioned2015-08-03T12:10:34Zen
dc.date.available2015-08-03T12:10:34Zen
dc.date.issued2014-10-14en
dc.identifier.issn18645631en
dc.identifier.doi10.1002/cssc.201402441en
dc.identifier.urihttp://hdl.handle.net/10754/563800en
dc.description.abstractThe 1,2-(CH2P(1-adamantyl)2)2C6H4 (dadpx) coordinated palladium complex [(dadpx)Pd(OTf)2] (1) is a catalyst precursor for the isomerizing methoxycarbonylation of the internal double bond of methyl oleate, with an unprecedented selectivity (96%) for the linear diester 1,19-dimethyl nonadecanedioate. Rapid formation of the catalytically active solvent-coordinated hydride species [(dadpx)PdH(MeOH)]+ (3-MeOH) is evidenced by NMR spectroscopy, and further isolation and X-ray crystal structure analysis of [(dadpx)PdH(PPh3)]+ (3-PPh3). DFT calculations of key steps of the catalytic cycle unravel methanolysis as the decisive step for enhanced selectivity and the influence of the rigid adamantyl framework on this step by destabilization of transition states of unselective pathways.en
dc.description.sponsorshipFinancing by the Stiftung Baden-Wurttemberg (Programm Umwelttechnologieforschung, U14) is acknowledged. P.R. gratefully acknowledges support from the Carl-Zeiss-Foundation by a graduate fellowship. Donation of high oleic sunflower oil methyl ester by Dako AG is acknowledged.en
dc.publisherWiley-Blackwellen
dc.subjectCarbonylationen
dc.subjectCatalysisen
dc.subjectIsomerizationen
dc.subjectRenewable resourcesen
dc.subjectSelectivityen
dc.titlePromotion of selective pathways in isomerizing functionalization of plant oils by rigid framework substituentsen
dc.typeArticleen
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentChemical Science Programen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.identifier.journalChemSusChemen
dc.contributor.institutionDepartment of Chemistry, University of KonstanzKonstanz, Germanyen
dc.contributor.institutionDepartment of Chemistry, University of SalernoFisciano, SA, Italyen
kaust.authorCavallo, Luigien
dc.relation.isSupplementedByChristl, J. T., Roesle, P., Stempfle, F., Müller, G., Caporaso, L., Cavallo, L., & Mecking, S. (2014). CCDC 992440: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc129q69en
dc.relation.isSupplementedByDOI:10.5517/cc129q69en
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624304en
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