623-30-3Relevant articles and documents
Study of the oxidative esterification of furfural catalyzed by Au25(glutathione)18 nanocluster deposited on zirconia
Shahin, Zahraa,Rataboul, Franck,Demessence, Aude
, (2020/11/24)
Au/ZrO2 catalyst prepared from Au25(SG)18 nanoclusters (SG stands for glutathione) deposited on ZrO2 has shown to be an efficient system for the oxidative esterification of furfural with methanol. The influence of the supported nanoclusters was studied and showed that partial calcination of the supported nanoclusters at 300 °C was sufficient for a quantitative formation of methyl-2-furoate even in the absence of a base. In the presence of 0.27 mol% of Au, initial activities up to 250 h?1 were obtained at 100 °C under 6 bar of O2. The reactivity was extended to the oxidative esterification of furfuryl alcohol and the formation of various products and intermediates was discussed.
A selective oxidative valorization of biomass-derived furfural and ethanol with the supported gold catalysts
Gao, Yiqi,Tong, Xinli,Zhang, Haigang
, p. 238 - 245 (2019/06/18)
The oxidative upgrading of renewable furfural (FUR) and ethanol is an important way to produce high-quality liquid fuel and value-added furanic derivatives. In this work, a series of supported Au catalysts were prepared using the colloid-immobilization technique, and further employed for catalytic oxidative condensation of FUR with ethanol in the presence of molecular oxygen. It is found that, with Au@CaO as the catalyst, 85.9% conversion of FUR and 81.8% selectivity of the product furan-2-acrolein were achieved in the absence of any homogeneous basic additive. The effects of different reactions such as reaction time, temperature and catalyst amount were explored in detail. Also, the influences of calcination temperature and amount of protective agent during the preparation of catalyst were investigated. According to the characterization results of catalyst, it is concluded that the synergistic effect of metallic Au and basic site of CaO support plays a significant role on the selective oxidative condensation. At last, a possible reaction mechanism is proposed based on the catalytic principle and experimental results.
Enantioselective Aldol Addition of Acetaldehyde to Aromatic Aldehydes Catalyzed by Proline-Based Carboligases
Biewenga, Lieuwe,Charnock, Simon J.,Guo, Chao,Poelarends, Gerrit J.,Saifuddin, Mohammad,Saravanan, Thangavelu
, p. 2522 - 2527 (2020/03/11)
Aromatic β-hydroxyaldehydes, 1,3-diols, and α,β-unsaturated aldehydes are valuable precursors to biologically active natural products and drug molecules. Herein we report the biocatalytic aldol condensation of acetaldehyde with various aromatic aldehydes to give a number of aromatic α,β-unsaturated aldehydes using a previously engineered variant of 4-oxalocrotonate tautomerase [4-OT(M45T/F50A)] as carboligase. Moreover, an efficient one-pot two-step chemoenzymatic route toward chiral aromatic 1,3-diols has been developed. This one-pot chemoenzymatic strategy successfully combined a highly enantioselective aldol addition step catalyzed by a proline-based carboligase [4-OT(M45T/F50A) or TAUT015] with a chemical reduction step to convert enzymatically prepared aromatic β-hydroxyaldehydes into the corresponding 1,3-diols with high optical purity (e.r. up to >99:1) and in good isolated yield (51-92%). These developed (chemo)enzymatic methodologies offer alternative synthetic choices to prepare a variety of important drug precursors.
Selective carbon-chain increasing of renewable furfural utilizing oxidative condensation reaction catalyzed by mono-dispersed palladium oxide
Tong,Zhang, Zhenya,Gao, Yiqi,Zhang, Yue,Yu, Linhao,Li, Yongdan
, (2019/08/12)
A novel carbon-chain increasing valorization of furfural (FUR), a cheap bio-based platform compound, has been successfully performed via the catalytic oxidative condensation process with mono-dispersed palladium oxide catalyst. For the reaction of furfural, n-propanol and O2, the PdO?TiO2 exhibited a prominent catalytic activity in which a 77.8% conversion of FUR with 89.2% selectivity of 3-(furan-2-yl)-2-methylacrylaldehyde was obtained. Based on the XRD, SEM, TEM, HRTEM, XPS, and UV–vis results of catalysts, it was concluded that high activity is associated with particle size, uniform distribution of palladium oxide and surface area of the support. Moreover, the recycling experiments confirmed that mono-dispersed palladium oxide catalyst was stable, in which it still kept a good catalytic performance after being recycled for five times. This provided a new route for the selective transformation of the hemicellulose-derived platform compounds.
A regulatable oxidative valorization of furfural with aliphatic alcohols catalyzed by functionalized metal-organic frameworks-supported Au nanoparticles
Ning, Liangmin,Liao, Shengyun,Liu, Xuguang,Guo, Pengfei,Zhang, Zhenya,Zhang, Haigang,Tong, Xinli
, p. 1 - 13 (2018/05/30)
The oxidative upgrading of furfural (FUR) and aliphatic alcohols is an important way to produce desirable precursor of jet fuel or value-added furanic compound. Therein, developing a highly active catalytic system with switchable product selectivity still remains a challenge. In this work, we report a novel strategy on regulating the oxidative condensation and oxidative esterification of FUR with aliphatic alcohol in the presence of molecular oxygen. Firstly, Au@UiO-66 is prepared using different methods and employed as the catalyst for the oxidative valorization of FUR with methanol. It is found that the impregnation-reduction-H2 (I-H) method is the best where a 100% selectivity of methyl-2-furoate with a complete conversion was obtained using Au@UiO-66 as catalyst. Then, a series of metal-organic frameworks (MOFs) supported Au nanoparticles (Au@UiO-66-X) such as Au@UiO-66, Au@UiO-66-NH2, Au@UiO-66-NO2, Au@UiO-66-COOH and Au@UiO-66-NH3Cl have been prepared with I-H method and employed for oxidative valorization of furfural with ethanol. Experimental results showed that, in “FUR-ethanol-O2” system, the Au@UiO-66-X can efficiently regulate the oxidative condensation and oxidative esterification as two competitive reaction pathways. With Au@UiO-66-COOH as the catalyst, the oxidative condensation process is dominant in which 84.1% selectivity of furan-2-acrolein is attained; Meanwhile, the Au@UiO-66 is beneficial to the occurrence of oxidative esterification and generation of ethyl-2-furoate. At last, based on the catalyst characterization and the numerous control experiments, a possible catalytic reaction mechanism for conversion of FUR is proposed.
Versatile catalysis of iron: Tunable and selective transformation of biomass-derived furfural in aliphatic alcohol
Zhang, Zhenya,Tong, Xinli,Zhang, Haigang,Li, Yongdan
, p. 3092 - 3100 (2018/07/13)
An iron-catalyzed efficient valorization of biomass-derived furfural (FUR) in aliphatic alcohols is developed in which product selectivity can be simply regulated by varying the gas atmosphere. In the presence of molecular oxygen, there is oxidative condensation of FUR with ethanol, and the obtained product is furan-2-acrolein in a "FUR-ethanol-O2" system. Under suitable conditions, the conversion of FUR and selectivity of furan-2-acrolein are 84.2% and 82.7%, respectively. In the presence of H2, the selective hydrogenation of FUR is achieved, and the main product is furfuryl alcohol in a "FUR-ethanol-H2" system. Under optimal conditions, a 99.9% conversion of FUR and 93.6% selectivity of furfuryl alcohol are attained. This provides an economic, green and sustainable method for the utilization of biomass-based platform compounds in the chemical industry.
Secondary amine-catalyzed [3 + 3] benzannulation to access polysubstituted benzenes through iminium activation
Jiang, Lin,Li, Hang,Zhou, Jiang-Feng,Yuan, Ming-Wei,Li, Hong-Li,Chuan, Yong-Ming,Yuan, Ming-Long
supporting information, p. 336 - 343 (2018/02/09)
An organocatalytic [3 + 3] benzannulation to access polysubstituted benzenes from readily available α,β-unsaturated aldehydes and 1,3-bis(phenylsulfonyl)propene or 4-sulfonylcrotonates is described. The key reaction step is considered to be the iminium ac
A method for utilizing high-efficiency catalytic oxidation of furfural and fatty alcohol preparation furan for fluoro method
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Paragraph 0012; 0013; 0015; 0017; 0019, (2018/04/20)
The invention discloses a method for preparing furyl aldehyde by using efficient catalytic oxidation of furfural and fatty alcohol. Furyl aldehyde is prepared from furfural as a substrate and supported nano gold as a catalyst. The method comprises the following specific steps: dissolving furfural into an organic solvent, adding to the supported nano gold and an assistant, and reacting at 25-170 DEG C for 1-15 hours in a 0.01-05MPa oxygen atmosphere under the condition that the stirring speed is 100-5,000r/min; and carrying out selective catalytic oxidation on furfural and fatty alcohol through the supported nano gold, so as to prepare furyl aldehyde. The preparation method is simple and easy to operate, generates few by-products and is friendly to environment. A supported nano gold catalyst is adopted, is mild in condition, good in catalysis effect, easy to recover, and can be repeatedly used; the supported nano gold catalyst can be used for efficiently catalyzing oxidation of furfural with high selectivity to generate furyl aldehyde; and the product is easy to separate, the production cost is low, and technical and economic effects are remarkable, and therefore the method has a good application prospect.
One-Pot l-Proline-Mediated Stereoselective α-C(sp2)–H Fluorination of α,β-Unsaturated Aldehydes through Methoxyfluorination–Elimination
Zhou, Jiadi,Jiang, Xinpeng,Jin, Can,Guo, Zhicheng,Su, Bin,Su, Weike
supporting information, p. 3631 - 3634 (2017/07/22)
A one-pot, two-step l-proline-mediated stereoselective α-C(sp2)–H fluorination of α,β-unsaturated aldehydes towards their corresponding (Z)-α-fluoro-α,β-unsaturated aldehydes has been developed. The first step utilises Selectfluor as a fluorinating agent in CH3NO2/MeOH forming (Z)-α-fluoro-α,β-unsaturated aldehydes and their corresponding dimethyl acetals through methoxyfluorination-elimination. In the second step, water is added to promote the hydrolytic cleavage of the dimethyl acetals. The obtained (Z)-α-fluoro-α,β-unsaturated aldehydes were smoothly reduced to the corresponding alcohols by using NaBH4.
Efficient and selective transformation of biomass-derived furfural with aliphatic alcohols catalyzed by a binary Cu-Ce oxide
Tong, Xinli,Yu, Linhao,Luo, Xuan,Zhuang, Xuli,Liao, Shengyun,Xue, Song
, p. 175 - 180 (2017/09/30)
The efficient transformation of furfural (FUR) with aliphatic alcohols to achieve the carbon-chain growth has been developed using a binary Cu-Ce oxide as the catalyst. In the presence of molecular oxygen, the tandem oxidative condensation of FUR with n-propanol is successfully performed, in which an 85.4% conversion of FUR in 95.3% selectivity of 3-(furan-2-yl-)-2-methylacryaldehyde was obtained. The effects of different Cu/Ce ratios and base additives were investigated in detail. As a result, it is found that the CuO-CeO2 (1: 9) catalyst is optimal and potassium carbonate is a suitable additive. Next, the recycling of CuO-CeO2 catalyst was tested and there is no obvious activity loss after being reused five times. Moreover, the oxidative condensation of FUR with various aliphatic alcohols including ethanol, isopropanol, n-butanol and n-hexanol was studied where the long chain alcoholic molecule hinders the proceeding of reaction. Finally, based on the experimental results and reaction phenomena, a possible mechanism for the oxidative condensation of FUR with n-propanol-O2 is proposed.
