Diels–Alder Reactions of Furans with Itaconic Anhydride: Overcoming Unfavorable Thermodynamics

Abstract

Unfavorable thermodynamics often render furans reluctant to engage in high-yielding Diels-Alder (DA) cycloaddition reactions. Here we report the highly efficient conversion of the bio-sourced reactants itaconic anhydride (IA) and furfuryl alcohol (FA) to a single DA adduct. The free energy advantages provided by anhydride ring-opening and crystal lattice energy of the product overcome the loss of aromaticity of the furanoid diene. Detailed 1H NMR studies provided valuable insights about relevant kinetic and thermodynamic features.

Rapid, Regioselective Living Ring‐Opening Metathesis Polymerization of Bio‐Derivable Asymmetric Tricyclic Oxanorbornenes

“…This has been recently illustrated by Bai et al where polymers were prepared, albeit slowly ( t > 24 h), by the ROMP of tricyclic endo , exo ‐functional DA adducts, derived from furfuryl alcohol and itaconic anhydride. An in‐depth mechanistic study of the formation of these tricyclic adducts via tandem Diels–Alder cycloaddition and lactonization has been recently reported by Pehere et al…”

Wholly biomass derivable sustainable polymers by ring-opening metathesis polymerisation of monomers obtained from furfuryl alcohol and itaconic anhydride

“…This observation was also reported independently and simultaneously by Hoye et al who were investigating the Diels-Alder addition of itaconic anhydride 6 to a range of furans. 27 Compound 7 is formed as a result of a tandem Diels-Alder cycloaddition and lactone formation, with the product crystallising from solution, or from the neat reaction mixture. It is believed that the Diels-Alder addition occurs rapidly and reversibly, as is typical of Diels-Alder additions to furans, 28,29,30 and that the second step is lactone formation, with the overall reaction being driven by the crystallisation of polycyclic oxanorbornene carboxylic acid 7.…”

Rapid Ring‐Opening Metathesis Polymerization of Monomers Obtained from Biomass‐Derived Furfuryl Amines and Maleic Anhydride

“…[10] In recent work, we were able to demonstrate that the reaction between itaconic anhydride 6 and furfuryl alcohol 4 proceeded cleanlya tr oom temperature to give acid 8 by ao ne-pot and 100 %a tom-economical tandem Diels-Alderlactone formation process requiringn oa dditional reagents, catalysts or solvents (Scheme1). [12] We also demonstrated that av ariety of esters and amides of acid 8 are good substrates for ring-openingm etathesis polymerization (ROMP) when using Grubbs second-generation catalyst 9.T he polymerizations displayed aw ell-controlled linear relationship between polymer molecular weight and monomer/catalyst ratio and were able to produce both random andb lock copolymers. [12] We also demonstrated that av ariety of esters and amides of acid 8 are good substrates for ring-openingm etathesis polymerization (ROMP) when using Grubbs second-generation catalyst 9.T he polymerizations displayed aw ell-controlled linear relationship between polymer molecular weight and monomer/catalyst ratio and were able to produce both random andb lock copolymers.…”

“…[11] The same result was obtained independently and simultaneously by the group of Hoye. [12] We also demonstrated that av ariety of esters and amides of acid 8 are good substrates for ring-openingm etathesis polymerization (ROMP) when using Grubbs second-generation catalyst 9.T he polymerizations displayed aw ell-controlled linear relationship between polymer molecular weight and monomer/catalyst ratio and were able to produce both random andb lock copolymers. [13] However,t he polymerization of these monomers was very slow,w ith at ypical reaction taking 72 ht or each completion.T his limited the variety of polymer architectures that could be produced as "dead"c hain ends become as ignificant problem over extended polymeri-Well-controlled and extremelyr apid ring-opening metathesis polymerization of unusualo xanorbornene lactam esters by Grubbs third-generation catalysti su sed to preparearange of bio-based homo-a nd copolymers.…”