title: Cross-metathesis of biosourced fatty acid derivatives: a step further toward improved reactivity.
abstract: The improved catalytic conversion of bioresources, namely unsaturated fatty acid derivatives, is presented. The targeted reaction is ruthenium-catalyzed cross-metathesis with functionalized olefins (α,β-unsaturated esters), that affords shorter diesters. These can be used as biosourced (pre)monomers for the production of polyesters. It is demonstrated that switch from terminal to internal cross-metathesis partners (that is, from methyl acrylate to methyl crotonate) allows use of ppm-level catalyst loadings, while retaining high productivity and selectivity. This was exemplified on a commercial biosourced fatty acid methyl esters mixture, using minimal purification of the substrate, on a 50 g scale. We propose that this improved catalytic behavior is due to the sole presence of more stable alkylidene intermediates, as the notoriously unstable ruthenium methylidene species are not formed using an internal functionalized olefin.
authors.affiliation: UCCS (CNRS-UMR 8181), Université Lille Nord de France, USTL-ENSCL, 59652 Villeneuve d'Ascq (France).
authors.forename: Paul
authors.initials: P
authors.lastname: Vignon
authors.forename: Tom
authors.initials: T
authors.lastname: Vancompernolle
authors.forename: Jean-Luc
authors.initials: JL
authors.lastname: Couturier
authors.forename: Jean-Luc
authors.initials: JL
authors.lastname: Dubois
authors.forename: André
authors.initials: A
authors.lastname: Mortreux
authors.forename: Régis M
authors.initials: RM
authors.lastname: Gauvin
mesh_terms: D002384:Catalysis; D005231:Fatty Acids, Unsaturated / Q000737:chemistry*; D012428:Ruthenium / Q000737:chemistry
chemical_list: D005231:Fatty Acids, Unsaturated; D012428:Ruthenium
keywords: cross-metathesis; fatty acid methyl esters; methyl crotonate; methyl oleate; ruthenium catalyst