Design and synthesis of selective complexes for olefin and alkyne metathesis
Keywords: Olefin metathesis, Ruthenium, NHC, Z-selectivity
Olefin metathesis is one of the most powerful methodologies for the formation of C-C double bonds, with tremendous successes in numerous fields of application, including natural product synthesis, oleo-chemistry and material science. Driven by the discovery of new ruthenium catalysts with improved performances, our group is involved in the exploration of new types of complex architectures, with the objective of proposing innovative solutions addressing specific issues relating to sustainable chemistry. Thus, a library of eco-efficient and highly selective Ru-complexes was developed and successfully applied in various transformations, often industrially relevant. Alkyne metathesis catalyzed by Mo and W-complexes is also being studied to provide highly valuable polyynes.
Contacts: Marc Mauduit, Christophe Crévisy,Sophie Rouen, Lucie Jarrige.
Functional polymer materials
Keywords: ring-opening metathesis polymerization (ROMP), non-isocyanate polyurethane (NIPU), polyhydroxyurethane (PHU), polysiloxanes, catalytic engineering
Polyurethanes (PUs) are currently industrially prepared from the polyaddition of diols with toxic diisocyanates. Current efforts towards the design of non-isocyanate PUs (NIPUs) mainly rely on the polyaddition of a 5-membered cyclic biscarbonate and a diamine, thereby affording polyhydroxyurethanes (PHUs). We have been developing α,ω-telechelic functional polyolefins, prepared by the tandem ring-opening metathesis (ROMP) / cross-metathesis (CM) polymerization of cyclic olefins, performed in the presence of a difunctionnal (FG = functional group = 5CC, 5-membered dithiocarbonate, azalactone, epoxide, oxetane, trialkoxysilyl) alkene chain transfer agent (CTA). Further polyaddition of such α,ω-difunctional polymers with di- or polyamines affords original NIPUs/PHUs. In particular, hydrolysis of α,ω-bis(trialkoxysilyl)telechelic polymers provide a 3-D network with valuable adhesives properties
Contacts: Sophie Guillaume, Jean-François Carpentier.
