Multifunctional Cascade Catalysis of Itaconic Acid Hydrodeoxygenation to 3‑Methyl-tetrahydrofuran

Hybrid production of isoprene from biomass-derived sugar as a feedstock for renewable rubber is a three-part process comprising glucose fermentation to itaconic acid, liquid-phase hydrodeoxygenation to 3-methyl-tetrahydrofuran, followed by vapor-phase dehydra-decyclization to isoprene. Here, we investigate a multifunctional catalyst design for itaconic acid hydrodeoxygenation to 3-methyl-tetrahydrofuran. The production of 3-methyl-tetrahydrofuran from itaconic acid is a multistep process involving hydrogenation, acid-catalyzed dehydration, and hydrodeoxygenation of multiple organic functionalities. A detailed kinetic analysis of this multistep reaction network over a Pd/C catalyst revealed a kinetic bottleneck in the reduction of methyl-γ-butyrolactone to 1,4-methylbutanediol, which was accelerated through the use of Re as an oxophillic promoter. Varying ratios of Pd:Re indicated a maximum overall rate of lactone ring opening with a 3.5:1.0 Pd:Re ratio, likely due to the combined capability of Pd to hydrogenate double bonds and Re to open the lactone ring. Applying this insight, the overall rate of itaconic acid hydrodeoxygenation to 3-methyl-tetrahydrofuran increased by more than an order of magnitude

Renewable Isoprene by Sequential Hydrogenation of Itaconic Acid and Dehydra-Decyclization of 3‑Methyl-Tetrahydrofuran

Catalytic hydrogenation of itaconic acid (obtained from glucose fermentation) yields 3-methyl-tetrahydrofuran (3-MTHF), which then undergoes catalytic dehydra-decyclization to isoprene. It is demonstrated that a one-pot cascade reaction converts itaconic acid to 3-MTHF at ∼80% yield with Pd–Re/C catalyst and 1000 psig H₂. Subsequent gas-phase catalytic ring opening and dehydration of 3-MTHF with phosphorus-containing zeolites including P-BEA, P-MFI, and P-SPP (self-pillared pentasil) exhibits 90% selectivity to dienes (70% isoprene, 20% pentadienes) at 20–25% conversion

Tunable Oleo-Furan Surfactants by Acylation of Renewable Furans

An important advance in fluid surface control was the amphiphilic surfactant composed of coupled molecular structures (i.e., hydrophilic and hydrophobic) to reduce surface tension between two distinct fluid phases. However, implementation of simple surfactants has been hindered by the broad range of applications in water containing alkaline earth metals (i.e., hard water), which disrupt surfactant function and require extensive use of undesirable and expensive chelating additives. Here we show that sugar-derived furans can be linked with triglyceride-derived fatty acid chains via Friedel–Crafts acylation within single layer (SPP) zeolite catalysts. These alkylfuran surfactants independently suppress the effects of hard water while simultaneously permitting broad tunability of size, structure, and function, which can be optimized for superior capability for forming micelles and solubilizing in water