Selective Decarbonylation of Fatty Acid Esters to Linear α-Olefins

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.