104-80-3Relevant articles and documents
Enzyme-catalyzed asymmetric acylation and hydrolysis of cis-2,5-disubstituted tetrahydrofuran derivatives: Contribution to development of models for reactions catalyzed by porcine liver esterase and porcine pancreatic lipase
Naemura,Fukuda,Takahashi,Konishi,Hirose,Tobe
, p. 911 - 918 (1993)
Pig liver esterase, lipase from porcine pancreas, lipase from Pseudomonas sp. (lipase YS), and lipase from Candida cylindracea catalyzed hydrolyses of the cis-diacetate 1 and the trans-diacetate (±)-4 to give the cis-monoacetate 3 and the trans-monoacetate 6 in optically active forms, respectively. Lipase YS-catalyzed acylations of the cis-diol 2 and the trans-diol (±)-5 with an acylating agent in cyclohexane yielded (-)-3 and (-)-6, respectively. The group adjacent to the R stereogenic center preferentially reacted in lipase YS-catalyzed hydrolyses of 1 and (±)-4 and acylations of 2 and (±)-5, and the enantioselectivites are rationalized by our rule recently proposed for lipase YS.
Catalytic Response and Stability of Nickel/Alumina for the Hydrogenation of 5-Hydroxymethylfurfural in Water
Perret, Noémie,Grigoropoulos, Alexios,Zanella, Marco,Manning, Troy D.,Claridge, John B.,Rosseinsky, Matthew J.
, p. 521 - 531 (2016)
The catalytic response of Ni on Al2O3 obtained from Ni-Al layered double hydroxides was studied for the liquid-phase hydrogenation of hydroxymethyl furfural to tetrahydrofuran-2,5-diyldimethanol (THFDM) in water. The successive calcination and reduction of the precursors caused the removal of interlayer hydroxyl and carbonate groups and the reduction of Ni2+ to Ni0. Four reduced mixed oxide catalysts were obtained, consisting of different amount of Ni metal contents (47-68 wt %) on an Al-rich amorphous component. The catalytic activity was linked to Ni content whereas selectivity was mainly affected by reaction temperature. THFDM was formed in a stepwise manner at low temperature (353 K) whereas 3-hydroxymethyl cyclopentanone was generated at higher temperature. Coke formation caused deactivation; however, the catalytic activity can be regenerated using heat treatment. The results establish Ni on Al2O3 as a promising catalyst for the production of THFDM in water.
Catalytic selective hydrogenation and rearrangement of 5-hydroxymethylfurfural to 3-hydroxymethyl-cyclopentone over a bimetallic nickel-copper catalyst in water
Zhang, Shujing,Ma, Hong,Sun, Yuxia,Luo, Yang,Liu, Xin,Zhang, Meiyun,Gao, Jin,Xu, Jie
, p. 1702 - 1709 (2019)
The selective hydrogenation and rearrangement of 5-hydroxymethylfurfural (5-HMF) to 3-hydroxymethyl-cyclopentone (HCPN) were studied over a MOF-derived bimetallic nickel-copper catalyst in water. The combination of nickel and copper dramatically improved the efficiency in both the selective hydrogenation of the carbonyl group of 5-HMF and the hydrogenative ring-rearrangement of the C5 ring, affording 70.3% yield for HCPN and 99.8% yield for the rearrangement products. Moreover, it was indicated that water acted as a solvent, reactant, and proton donor by dissociation at an elevated temperature, which supplied slightly acidic conditions and promoted the rearrangement reaction.
Selective hydrogenation of aromatic furfurals into aliphatic tetrahydrofurfural derivatives
Chen, Bingfeng,Han, Buxing,Li, Shaopeng,Liu, Huizhen,Shen, Xiaojun,Wang, Yanyan,Yang, Youdi
, p. 4937 - 4942 (2020)
Tetrahydrofurfural (THFF) and 5-hydroxymethyltetrahydro-2-furaldehyde (5-HMTHFF) are important chemicals. Synthesis of THFF and 5-HMTHFF from the selective hydrogenation of furfural (FF) and 5-hydroxymethylfurfural (HMF) is highly desirable. However, it is a great challenge to hydrogenate furanyl rings while keeping CO intact. Herein, we found that Pd/LDH-MgAl-NO3 could efficiently catalyze the hydrogenation of FF to THFF and HMF to 5-HMTHFF in water. At near complete conversion of FF and HMF, the selectivities of THFF and 5-HMTHFF could reach 92.6% and 83.7%, respectively. A series of control experiments showed that both the LDH-MgAl-NO3 support and water solvent played an important role in the unusual performance of the catalytic system. The hydrogenation of the furanyl ring occurred on the surface of Pd. Water prohibited the hydrogenation of the CO group, and the special nature of LDH-MgAl-NO3 prevented hydrogenation of the CO group on the support by the hydrogen spillover. Thus, the furanyl ring was selectively hydrogenated, and high selectivity of the desired product was successfully achieved. As far as we know, efficient hydrogenation of FF to THFF or HMF to 5-HMTHFF has not been reported. This work opens the way to selectively hydrogenate the furanyl ring while keeping CO in the same molecule unchanged. This journal is
Combination of Pd/C and Amberlyst-15 in a single reactor for the acid/hydrogenating catalytic conversion of carbohydrates to 5-hydroxy-2,5- hexanedione
Liu, Fei,Audemar, Maite,De Oliveira Vigier, Karine,Clacens, Jean-Marc,De Campo, Floryan,Jerome, Francois
, p. 4110 - 4114 (2014)
Here we show that combination of Pd/C and Amberlyst-15 in a single reactor allowed fructose and inulin to be converted to 5-hydroxy-2-5-hexanedione, a valuable chemical platform, in a one-pot process. the Partner Organisations 2014.
Palladium/carbon dioxide cooperative catalysis for the production of diketone derivatives from carbohydrates
Liu, Fei,Audemar, Ma?té,De Oliveira Vigier, Karine,Clacens, Jean-Marc,De Campo, Floryan,Jér?me, Fran?ois
, p. 2089 - 2093 (2014)
The one-pot production of industrially valuable diketone derivatives from carbohydrates is achieved through a bifunctional catalytic process. In particular, Pd/C-catalyzed hydrogenation of HMF in water and under CO 2 affords 1-hydroxypentane-2,5-dione with up to 77 % yield. The process is also eligible starting from fructose and inulin, affording 1-hydroxyhexane-2,5-dione with 36 % and 15 % yield, respectively. The key of the process is reversible in situ formation of carbonic acid, which is capable of assisting Pd/C during the hydrogenation reaction by promoting the dehydration of carbohydrates and the ring-opening of furanic intermediates. Interestingly, by changing the reaction medium from H2O to a H2O/THF mixture (1:9), it is possible to switch the selectivity of the reaction and to produce 2,5-hexanadione with 83 % yield. Within the framework of sustainable chemistry, reactions presented in this report show 100 % carbon economy, involve CO 2 to generate acidity, require water as a solvent, and are conducted under rather low hydrogen pressures (10 bar).
Homogeneous catalysed hydrogenation of HMF
Cadu, Alban,Sekine, Kohei,Mormul, Jaroslaw,Ohlmann, Dominik M.,Schaub, Thomas,Hashmi, A. Stephen K.
, p. 3386 - 3393 (2018)
In this report, hydroxymethylfurfural (HMF) is used as a bio-based feedstock for homogeneous metal-catalysed hydrogenation. Several ligand classes and metals are employed to reduce the aldehyde and aromatic ring of HMF. The previously unknown homogeneous catalysed hydrogenation of HMF to tetrahydrofuran-dimethanol (THFDM) was investigated using different catalyst systems. NHCs and phosphites give higher trans/cis ratios (between 1:1.25 and 1:3.95) of the product THFDM, but low conversions of only up to 17% accompanied by up to 92% yield of bis(hydroxymethyl)furan at 10 bar H2 and 120 °C. Conversely, di-phosphine ligated ruthenium catalysts in up to 87% yield lead to the highest overall conversion but only moderate trans/cis ratios of only 1:3.1-1:5.
Immobilized Ru clusters in nanosized mesoporous zirconium silica for the aqueous hydrogenation of furan derivatives at room temperature
Chen, Jiazhi,Lu, Fang,Zhang, Junjie,Yu, Weiqiang,Wang, Feng,Gao, Jin,Xu, Jie
, p. 2822 - 2826 (2013)
Ru lonesome tonight? Immobilized ruthenium clusters (50Ru atoms) in nanosized mesoporous zirconium silica were synthesized by using an impregnation method starting from an aqueous solution of RuCl3. The Ru cluster catalysts were thermally stable at 500°C and showed remarkable activity for the hydrogenation of furan derivatives in water at room temperature under 5bar hydrogen pressure.
Biomass into chemicals: One-pot production of furan-based diols from carbohydrates via tandem reactions
Cai, Haile,Li, Changzhi,Wang, Aiqin,Zhang, Tao
, p. 59 - 65 (2014)
In this work, the direct production of furan-based diols from carbohydrates and their upstream raw materials via one-pot tandem reactions in ionic liquid/water system is presented. In this novel reaction system, ionic liquid serves as an advantageous solvent for polysaccharide (cellulose, inulin, sucrose) hydrolysis and hexose dehydration reactions, and heterogeneous Pd, Pt, Ir, Ni, Ru-based catalysts catalyze HMF hydrogenation reaction under relatively mild condition (50 °C, 6 MPa H2) to afford moderate to high yield (34.0-89.3%) of furan-based diols, namely, 2,5-dihydroxymethylfuran (DHMF) and 2,5-dihydroxymethyltetrahydrofuran (DHMTF). Our results show that the metal species strongly affects the selectivity of the products, while the nature of the support influences the activity of the catalysts significantly. By selecting the proper metal species and the support, controllable production of DHMF or DHMTF was realized. Based on the intermediates identified and the conversion results, the proposed reaction pathway, including possible side reactions were presented. Taken together, our catalytic system featured with simple process, mild condition, high yield of diols and adjustable product selectivity. The direct conversion of the carbohydrates and the upstream materials drives our technology nearer to real application for cost-efficient production of chemicals from biomass.
Highly efficient hydrogenative ring-rearrangement of furanic aldehydes to cyclopentanone compounds catalyzed by noble metals/MIL-MOFs
Li, Xiang,Deng, Qiang,Zhang, Likang,Wang, Jun,Wang, Rong,Zeng, Zheling,Deng, Shuguang
, p. 152 - 158 (2019)
Hydrogenative ring-rearrangement reaction of biomass-derived furanic aldehydes to cyclopentanone compounds catalyzed by metal/support bifunctional catalysts suffers a low selectivity of target product and serious carbon loss because of the Br?nsted acid catalysis. Herein, a series of pure Lewis acid sites MIL-MOFs (Fe-MIL-100, Fe-MIL-101 and Cr-MIL-101) with different crystal topology structures and metals are synthesized. Then the nanoparticles of Ru, Pt, Pd and Au are uniformly dispersed on the internal surface of the MOF support. The hydrogenation rate catalyzed by the noble metals/Fe-MIL-100 is three times faster than those obtained with Fe-MIL-101 and Cr-MIL-101-based catalysts due to the higher dispersion of nanoparticles on the former to make it more accessible to reactants. Meanwhile, both of the noble metals on Fe-MIL-100 and Fe-MIL-101 have a higher selectivity of cyclopentanone compounds than that on Cr-MIL-101, since the Fe ions in the MOF host with a higher oxophilicity will promote the adsorption and hydrolysis of the intermediate furanic alcohols (furfural alcohol or 2,5-bis(hydroxymethyl)furan). Furthermore, the noble metals/MIL-MOFs catalyst can maintain a good activity and stability after recycling for five runs. The current work will present an efficient catalytic reaction system for the hydrogenative ring-rearrangement of furfural and 5-hydroxymethyl furfural to synthesize cyclopentanone compounds.
