Double-metal cyanide-supported Pd catalysts for highly efficient hydrogenative ring-rearrangement of biomass-derived furanic aldehydes to cyclopentanone compounds

Hydrogenative Ring-Rearrangement of Furfural to Cyclopentanone over Pd/UiO-66-NO2 with Tunable Missing-Linker Defects

“…For comparison, the FAL conversion and CPO selectivity over Pd/UiO-66- 7 was much lower compared to Pd/UiO-66-NO 2 - 7 . Form literature, it is known that a stronger Lewis acidity is beneficial for the hydrogenation and rearrangement process, or in other words, it improves the selectivity to CPO [ 14 , 21 , 22 ].…”

“…Various noble metals (Pd, Pt, Ru) and transition metals (Cu, Ni, Co) based catalysts have been demonstrated to be able to catalyze the hydrogenative ring-rearrangement of FAL to CPO [ 14 , 15 , 16 , 17 ]. Among them, Pd-based catalysts (Pd/C [ 18 ], Pd/f-SiO 2 [ 19 ], Pd/Y 2 (Sn 0.65 Al 0.35 ) 2 O 7−δ /Al 2 O 3 [ 20 ], Pd/Y 2 (Sn 7 Al 0.3 ) 2 O 7−δ [ 21 ], Pd/FeZn-DMC [ 22 ]) showed a good performance under mild conditions. It has been shown that Lewis acidity is a key factor in promoting the rearrangement of furan rings and achieving a high selectivity to CPO, whereas the Brønsted acid sites promote the polymerization to produce undesired products [ 23 ].…”

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

“…Cyclopentanone (CPO) is a versatile compound derived from furfural, which is widely used in the synthesis of fuels, pharmaceuticals, rubber chemicals, fungicides, and avor and fragrance chemicals. [113][114][115][116] It is well-accepted that the most important reaction step in the conversion of furfural to cyclopentanone is the hydrogenative ring-rearrangement of furfural, but the reaction mechanism is still under debate, and various reaction routes and reaction intermediates have been proposed, which may be dependent on the catalyst type, reaction conditions, etc. [116][117][118][119][120][121] In general, furfural is rstly hydrogenated to produce furfuryl alcohol, followed by a ring-opening reaction to give 2-pentene-1,4-dione (2-PED) accompanied by the formation of a tetrahydrofurfuryl alcohol (THFA) byproduct.…”

“…115,130 In addition to Cu-based catalysts, other noble metal catalysts also possess appreciable activity for the generation of CPO from furfural. 114,116,120,[124][125][126][134][135][136] Anatase TiO 2 -supported Au nanoparticles were found to effectively inhibit the side reaction and achieve nearly 100% CPO yield in the conversion of furfural to CPO. 134 Deng et al showed that a double-metal cyanide (DMC)-supported bi-functional Pd catalyst had high efficiency for the hydrogenative ring-rearrangement of furfural to cyclopentanone.…”

Highly Controllable Hydrogenative Ring Rearrangement and Complete Hydrogenation Of Biobased Furfurals over Pd/La2B2O7 (B=Ti, Zr, Ce)

“…[1][2][3][4][5][6] Due to the highly unsaturated state of furanic aldehydes, hydrotreatment is the most common transformation used to synthesize a wide range of high-value chemicals, including linear alcohols (1,5-pentanediol, 1,2-pentanediol, 1,2,5-pentanetriol, and 1,6-hexanediol), furanic alcohols (2-hydroxymethyl furan and 2,5-dihydroxymethyl furan), methylfurans (2-methylfuran and 2,5-dimethylfuran), tetrahydrofuran alcohols (2,5-dihydroxymethyltetrahydrofuran and 2hydroxymethyltetrahydrofuran), cyclopentanones (3hydroxymethyl cyclopentanone and cyclopentanone), and cyclopentanols (3-hydroxymethyl cyclopentanol and cyclopentanol). [7][8][9][10][11][12][13][14][15][16] Among these fine chemicals, cyclopentanones are important feedstocks for lysine, resins, biofuels, and vitamins, [17][18] and tetrahydrofuran alcohols are widely used as solvents, or building blocks of polyesters, polyethers, and adhesives. [19] The complex chemical group of furanic aldehydes provides great opportunity to synthesize these chemicals, but at the same time makes selective synthesis of target product very challenging.…”