Promotion of selective pathways in isomerizing functionalization of plant oils by rigid framework substituents
Type
ArticleAuthors
Christl, Josefine T.Roesle, Philipp
Stempfle, Florian
Müller, Gerhard J.
Caporaso, Lucia

Cavallo, Luigi

Mecking, Stefan
KAUST Department
Chemical Science ProgramKAUST Catalysis Center (KCC)
Physical Science and Engineering (PSE) Division
Date
2014-10-14Online Publication Date
2014-10-14Print Publication Date
2014-12Embargo End Date
2015-10-14Permanent link to this record
http://hdl.handle.net/10754/563800
Metadata
Show full item recordAbstract
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.Citation
Christl, J. T., Roesle, P., Stempfle, F., Müller, G., Caporaso, L., Cavallo, L., & Mecking, S. (2014). Promotion of Selective Pathways in Isomerizing Functionalization of Plant Oils by Rigid Framework Substituents. ChemSusChem, 7(12), 3491–3495. doi:10.1002/cssc.201402441Sponsors
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.Publisher
WileyJournal
ChemSusChemRelations
Is Supplemented By:- [Dataset]
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: 10754/624304
ae974a485f413a2113503eed53cd6c53
10.1002/cssc.201402441