Looking for the Noncyclic(amino)(alkyl)carbene Ruthenium Catalyst for Ethenolysis of Ethyl Oleate: Selectivity Is on Target

A wide set of 65 diverse Ru metathesis catalysts was investigated in the ethenolysis reaction of biosourced ethyl oleate to allow the comparison between the catalyst structure and its activity and selectivity. Handling of the oleic substrate, weighing of the catalysts, and charging the reactor were done in air, with exclusion of a glovebox or Schlenk techniques. A catalyst bearing the unsymmetrical N-heterocyclic ligand featuring a thiophene fragment (Ru-63) was selected to offer the best combination between high selectivity and sufficient activity under conditions mimicking oil industry practice. A proof-of-concept large-scale ethenolysis experiment was also done with the selected catalyst to prove its high selectivity at the 1 L scale reaction with a 90% pure non-distilled substrate.