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

Josefine T. Christl, Philipp Roesle, Florian Stempfle, Gerhard J. Müller, Lucia Caporaso, Luigi Cavallo, Stefan Mecking

Research output: Contribution to journalArticlepeer-review

17 Scopus citations


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.
Original languageEnglish (US)
Pages (from-to)3491-3495
Number of pages5
Issue number12
StatePublished - Oct 14 2014

Bibliographical note

KAUST Repository Item: Exported on 2020-10-01
Acknowledgements: 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.

ASJC Scopus subject areas

  • Energy(all)
  • Environmental Chemistry
  • Materials Science(all)
  • Chemical Engineering(all)


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