A comprehensive mechanistic picture of the isomerizing alkoxycarbonylation of plant oils

Philipp Roesle, Lucia Caporaso, Manuel Schnitte, Verena Goldbach, Luigi Cavallo, Stefan Mecking

Research output: Contribution to journalArticlepeer-review

99 Scopus citations


Theoretical studies on the overall catalytic cycle of isomerizing alkoxycarbonylation reveal the steric congestion around the diphosphine coordinated Pd-center as decisive for selectivity and productivity. The energy profile of isomerization is flat with diphosphines of variable steric bulk, but the preference for the formation of the linear Pd-alkyl species is more pronounced with sterically demanding diphosphines. CO insertion is feasible and reversible for all Pd-alkyl species studied and only little affected by the diphosphine. The overall rate-limiting step associated with the highest energetic barrier is methanolysis of the Pd-acyl species. Considering methanolysis of the linear Pd-acyl species, whose energetic barrier is lowest within all the Pd-acyl species studied, the barrier is calculated to be lower for more congesting diphosphines. Calculations indicate that energy differences of methanolysis of the linear versus branched Pd-acyls are more pronounced for more bulky diphosphines, due to involvement of different numbers of methanol molecules in the transition state. Experimental studies under pressure reactor conditions showed a faster conversion of shorter chain olefin substrates, but virtually no effect of the double bond position within the substrate. Compared to higher olefins, ethylene carbonylation under identical conditions is much faster, likely due not just to the occurrence of reactive linear acyls exclusively but also to an intrinsically favorable insertion reactivity of the olefin. The alcoholysis reaction is slowed down for higher alcohols, evidenced by pressure reactor and NMR studies. Multiple unsaturated fatty acids were observed to form a terminal Pd-allyl species upon reaction with the catalytically active Pd-hydride species. This process and further carbonylation are slow compared to isomerizing methoxycarbonylation of monounsaturated fatty acids, but selective.
Original languageEnglish (US)
Pages (from-to)16871-16881
Number of pages11
JournalJournal of the American Chemical Society
Issue number48
StatePublished - Nov 21 2014

Bibliographical note

KAUST Repository Item: Exported on 2020-10-01
Acknowledgements: P.R. gratefully acknowledges support from the Carl-Zeiss-Foundation by a graduate fellowship. We thank Dako AG for donation of high-oleic sunflower oils.

ASJC Scopus subject areas

  • Biochemistry
  • Colloid and Surface Chemistry
  • General Chemistry
  • Catalysis


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