Selective Decarbonylation of Fatty Acid Esters to Linear α-Olefins

Alex John, Büsra Dereli, Manuel A. OrtunÌo, Hillis E. Johnson, Marc A. Hillmyer, Christopher J. Cramer, William B. Tolman

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12 Scopus citations

Abstract

Selective decarbonylation of p-nitrophenol esters of fatty acids to the corresponding linear α-olefins (LAOs) was achieved using palladium catalysis. After extensive ligand screening, a mixed-ligand system exploiting the trans-spanning diphosphine XantPhos and an N-heterocyclic carbene (IPr) was identified as the most effective in yielding high α-selectivity and high conversions of the ester (>98% selectivity, >90% conversion using 2.5 mol % of PdCl2 and 5 mol % of the ligands, 190 °C, 2-2.5 h). On the basis of insights from modeling at the density functional level of theory, we propose that the mixed-ligand set achieves high α-selectivity by promoting olefin dissociation from the palladium center following β-hydride elimination, which is especially facilitated both by the combined steric bias of the mixed-ligand set and by the ability of the XantPhos ligand to coordinate in both mono- and bidentate fashions.

Original languageEnglish (US)
Pages (from-to)2956-2964
Number of pages9
JournalOrganometallics
Volume36
Issue number15
DOIs
StatePublished - Aug 14 2017

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