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

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.
Original languageEnglish (US)
Pages (from-to)3491-3495
Number of pages5
JournalChemSusChem
Volume7
Issue number12
DOIs
StatePublished - Oct 14 2014

ASJC Scopus subject areas

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

Fingerprint Dive into the research topics of 'Promotion of selective pathways in isomerizing functionalization of plant oils by rigid framework substituents'. Together they form a unique fingerprint.

Cite this