Catalytic carbonylation of renewable furfural derived 5-bromofurfural to 5-formyl-2-furancarboxylic acid in oil/aqueous bi-phase system

Aqueous Carbonylation of Furfural-Derived 5-Bromofuroic Acid to 2,5-Furandicarboxylic Acid with Supported Palladium Catalyst

“…Similar to what was observed in homogeneous conditions, both FDCA and FA were produced in the heterogeneous conditions disclosed in the present study. Accordingly, a similar carbonylation mechanism is proposed for the Pd­(Xantphos)­Cl 2 /AC catalyzed FDCA synthesis from 5-bromofurioc acid (Scheme ).…”

“…Meanwhile, other protocols based on disproportionation or CO 2 insertion involved the C–H bond activation of furoic acid under harsh conditions to afford FDCA. − Regarding the low efficiency in C–H activation of furfural for one-step oxidative carbonylation, an alternative protocol is preactivation of C–H bond prior to furfural carbonylation to the bifunctionalized product. Recently, we explored a new synthetic route to FDCA involving the homogeneous carbonylation of furfural-derived 5-bromofuroic acid under gentle conditions. − 5-Bromofuroic acid is currently employed as an intermediate in pharmaceutical synthesis; hence, it is industrially available through the bromination of furoic acid with liquid bromine, yet in a very limited volume. Although Br-substituted furan is not a common feedstock in biorefinery, in view of the ongoing industrial availability of 5-bromofuroic acid, it may function as a good platform to transform monofunctionalized furfural to bifunctionalized monomers for polymer synthesis.…”

Catalytic Transformation of the Furfural Platform into Bifunctionalized Monomers for Polymer Synthesis

“…In general, 5-formyl-2-furancarboxylic acid is an intermediate in HMF oxidation to FDCA, and it can also be synthesized through selective HMF oxidation . Inspired by their bromination–carbonylation route of FDCA synthesis, Yin explored a similar carbonylation route for the 5-formyl-2-furancarboxylic acid synthesis from 5-bromofurfural . In an oil/aqueous biphasic system, using 1 mol % PdCl 2 /Xantphos as the catalyst, the authors achieved a 99% yield of 5-formyl-2-furancarboxylic acid under 10 atom of CO in 36 h at 343 K. The carbonylation reaction happened in the oil phase.…”

“…200 Inspired by their bromination−carbonylation route of FDCA synthesis, Yin explored a similar carbonylation route for the 5-formyl-2furancarboxylic acid synthesis from 5-bromofurfural. 201 In an oil/aqueous biphasic system, using 1 mol % PdCl 2 /Xantphos as the catalyst, the authors achieved a 99% yield of 5-formyl-2furancarboxylic acid under 10 atom of CO in 36 h at 343 K. The carbonylation reaction happened in the oil phase. After the reaction, the generated 5-formyl-2-furancarboxylic acid salt was naturally transferred to the aqueous phase because of its hydrophilicity, thus achieving the product separation from the substrate and catalyst.…”

Feasible Synthesis of a Bifuran-Based Monomer for Polymer Synthesis from a Hemicellulose-Derived Platform

“…To pursue this goal, we have explored catalytic aerobic oxidations of furfural to maleic acid/anhydride, − and others explored H 2 O 2 -based oxidation of furfural to maleic acid, − the significant monomers in the polymer industry. Most recently, we further explored catalytic carbonylation of furfural-derived 5-bromofuroic acid (BFA) to 2,5-furandicarboxylic acid, − which provides a furfural-based route for 2,5-furandicarboxylic acid synthesis. Currently, BFA has been industrially produced through bromination of furoic acid for pharmaceutical synthesis; , however, because of the limited market volume of pharmaceutical production, it apparently blocks the BFA-based furfural utilizations in a large scale.…”