Selective Hydrogenolysis of Furfural Derivative 2‐Methyltetrahydrofuran into Pentanediol Acetate and Pentanol Acetate over Pd/C and Sc(OTf)₃ Cocatalytic System

Abstract

It is of great significance to convert platform molecules and their derivatives into high value-added alcohols, which have multitudinous applications. This study concerns systematic conversion of 2-methyltetrahydrofuran (MTHF), which is obtained from furfural, into 1-pentanol acetate (PA) and 1,4-pentanediol acetate (PDA). Reaction parameters, such as the Lewis acid species, reaction temperature, and hydrogen pressure, were investigated in detail. H NMR spectroscopy and reaction dynamics study were also conducted to help clarify the reaction mechanism. Results suggested that cleavage of the primary alcohol acetate was less facile than that of the secondary alcohol acetate, with the main product being PA. A PA yield of 91.8 % (150 °C, 3 MPa H , 30 min) was achieved by using Pd/C and Sc(OTf) as a cocatalytic system and an 82 % yield of PDA was achieved (150 °C, 30 min) by using Sc(OTf) catalyst. Simultaneously, the efficient conversion of acetic esters into alcohols by simple saponification was carried out and led to a good yield.

Development of the Applications of Palladium on Charcoal in Organic Synthesis

“…The hydrogenolysis reaction resulting from the cleavage of C–C, C–O and C–X bonds (X=I, Br, Cl or other element) by hydrogen gas or other hydrogen sources, is an efficient synthetic method, as exemplified by the hydrogenolysis of glycerol to ethylene and propylene glycol. It also has a great potential of applications in the conversion of further biomass‐derived polyols, including sugars or sugar alcohols . Therefore, a range of suitable catalyst systems has been developed .…”

W(OTf)6‐Catalyzed Synthesis of γ‐Lactones by Ring Contraction of Macrolides or Ring Closing of Terminal Hydroxyfatty Acids in Ionic Liquid

“…Thist rend is in accordance witht he effective charge density of the metal triflate. [14] The cation in the metal triflate with highere ffective charge density was very lacking in chargea nd had stronger Lewisa cidity, [15][16][17] which was furtherp roven by testing of metal triflates with the same central metal at differentv alences.T he catalytic activityo f Fe(OTf) 3 was better than that of Fe(OTf) 2 ,a sw as that of Ce(OTf) 4 in comparison to Ce(OTf) 3 .…”

Recent advances in the conversion of furfural into bio-chemicals through chemo- and bio-catalysis

“…Pentanediol, which is considered to be a promising bio-fuel, monomer of polyesters, and ne chemical intermediate, can be generated via the one-pot reaction of furfural or the hydrogenolysis of THFA. [137][138][139] However, compared to THFA hydrogenolysis, the direct transformation of furfural to pentanediol is more challenging because it is very difficult to achieve high selectivity toward pentanediol and it tends to yield many byproducts. 138,140 Much effort has been focused on exploring some novel catalysts for the hydrogenolysis of furfural to pentanediol.…”