Acid-Catalyzed Activation and Condensation of the =C5H Bond of Furfural on Aldehydes, an Entry Point to Biobased Monomers.

Furfural is an industrially relevant biobased chemical platform. Unlike classical furan, or C-alkylated furans, which have been previously described in the current literature, the =C5H bond of furfural is unreactive. As a result, on a large scale, C=C and C=O bond hydrogenation/hydrogenolysis is mainly performed, with furfuryl alcohol and methyl tetrahydrofuran being the two main downstream chemicals. Here, we show that the derivatization of the -CHO group of furfural restores the reactivity of its =C5H bond, thus permitting its double condensation on various alkyl aldehydes. Overcoming the recalcitrance of the =C5H bond of furfural has opened an access to a biobased monomer, whose potential have been investigated in the fabrication of renewably-sourced poly(silylether). By means of a combined theoretical-experimental study, a reactivity scale for furfural and its protected derivatives against carbonylated compounds has been established using an electrophilicity descriptor, a means to predict the molecular diversity and complexity this pathway may support, and also to de-risk any project related to this topic. Finally, by using performance criteria for industrial operations in the field of fuels and commodities, we discussed the industrial potential of this work in terms of cost, E-factor, reactor productivity and catalyst consumption.

One-Pot Catalysis: A Privileged Approach for Sustainable Polymers?

Almost all aspects of daily life involve polymers in some form or the other. However, polymer production is largely based on finite feedstocks. These limitations combined with environmental concerns force us to rethink the strategies for the synthesis of these materials. As an abundant and renewable resource, biomass is composed of a very diverse range of molecules that deserve to be valorized. The development of new methods for transforming biomass into resources suitable for polymer production remains a crucial hurdle on the road to a more sustainable chemical economy. The main challenge is to design efficient and selective transformations of abundant and inexpensive raw materials into innovative polymers. For the chemical industry to meet these challenges, process intensification must play an important role in developing cleaner and more energy-efficient technologies while aiming for safer and more sustainable processes. Catalysis is an important tool to support more sustainable plastics production by being ideally efficient, practical, and versatile. In this regard, the creation of sustainable polymers through one-pot catalysis represents an exciting frontier in materials science.In this Account, we describe some of the published advances for achieving one-pot synthesis of biobased monomers and the resulting (co)polymers. These studies demonstrate that one-pot reactions can produce sustainable materials for a wide range of applications. We show that these new multistep "one-pot" approaches are very promising from an academic and industrial point of view. These synthetic schemes have indeed allowed us to investigate the formation of new polyesters, polypeptides, and poly(meth)acrylates by different polymerization mechanisms. We discuss their efficiency by highlighting their ability to perform multiple (quantitative) synthetic transformations and bond formation steps while bypassing multiple purification procedures at the same time. While enabling the development of novel polymeric structures, we demonstrate that these one-pot procedures can also contribute to reducing the environmental footprint.In light of the growing concerns for sustainable development, these procedures may therefore allow, in the near future, one to prepare sustainable polymeric materials with advanced properties through extremely simplified routes from renewable feedstocks. Among these materials, block and alternating copolymers are unique structures that can exhibit a wide range of properties. While their multistep synthesis remains a demanding process, the one-pot synthesis of these polymers is much more scalable and can create multiblock or alternating copolymers with a wide range of potential sequences. These approaches then give access to materials whose structure and functionality can be designed to suit the need.

Titanium complexes of pyrrolylaldiminate ligands and their exploitation for the ring-opening polymerization of cyclic esters.

A series of six-coordinate titanium complexes 1-6 supported by pyrrolylaldiminate ligands were prepared via the reaction of 2 equivalents of ligands and Ti(OiPr)4 in toluene at 70 °C. The X-ray structure of 2 revealed that the two ligands were κ2-coordinated to the titanium center with the two pyrrole nitrogen atoms in trans positions and the two imine nitrogen atoms in cis positions. All complexes were active initiators for the ring-opening polymerization (ROP) of rac-lactide (rac-LA), ε-caprolactone (ε-CL), and three substituted ε-caprolactones (γ-methyl-ε-caprolactone (γMeCL), γ-ethyl-ε-caprolactone (γEtCL), and γ-phenyl-ε-caprolactone (γPhCL)). Polymerizations of all monomers were well controlled, affording predetermined molar masses and narrow dispersity values. Complex 5 exhibited the highest polymerization activities with rac-LA and ε-CL and its performance was comparable to other highly active six-coordinate titanium complexes reported thus far. Kinetic results revealed a first-order dependency on the monomer concentration, and the rate of polymerization was greatly influenced by the substituent on the imine nitrogen. End-group analysis of the isolated PLA and PCL suggested a coordination-insertion mechanism.