Polyketoesters from oleic acid. Synthesis and functionalization

In this study, we exploited the reactivity of the methyl oleate enone derivative for the conversion of this renewable raw material to ketone-containing hydroxyesters. The radical-mediated thiol–ene addition to the conjugated double bonds has been investigated and low yields were obtained due to secondary reactions. The thiol-Michael addition under acidic and basic/nucleophilic conditions was also examined. While using vanadyl triflate (VO(OTf)₂), a slight excess of thiol was necessary to complete the reaction, by using both basic/nucleophilic catalysts 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), quantitative conversion was achieved under stoichiometric conditions in shorter reaction times. The obtained hydroxyester, carrying sulphide and ketone functional groups, was used to obtain polyesters by Novozyme-435 enzymatic polymerization. The coupling between the ketone group of the repeating unit and a model oxyamine has been used to demonstrate the polyketoester functionalization via oxime formation.