7681-84-7Relevant academic research and scientific papers
Low-pressure Selective Hydroformylation of 2,3- and 2,5-Dihydrofuran with a Rhodium Catalyst. Unexpected Influence of the Auxiliary Ligand Tris(o-t-butylphenyl) Phosphite
Polo, A.,Real, J.,Claver, C.,Castillon, S.,Bayon, J. C.
, p. 600 - 601 (1990)
Hydroformylation of 2,3- and 2,5-dihydrofuran has been achieved in excellent yields and good selectivities under mild conditions using 2(cod)2> and suitable auxiliary ligands (cod = cyclo-octa-1,5-diene).
Effect of solvent nature on the catalytic hydroformylation of 2,3-dihydrofuran
Wol'F,Vartanyan,Lapidus
, p. 194 - 196 (2013)
The effect of the solvent nature on the process of hydroformylation of 2,3-dihydrofuran in the presence of the phosphine-containing, complex Rh catalyst HRh(CO)(PPh3)3 has been studied. The influence of solvent polarity and basicity on the conversion of 2,3-dihydrofuran has been revealed, and the composition of tetrahydrofuran aldehydes and the selectivity of their formation have been determined.
High-Temperature Synthesis of Carbon-Supported Bimetallic Nanocluster Catalysts by Enlarging the Interparticle Distance
Zuo, Lu-Jie,Xu, Shi-Long,Wang, Ao,Yin, Peng,Zhao, Shuai,Liang, Hai-Wei
supporting information, p. 2719 - 2723 (2022/02/16)
Supported bimetallic nanoparticle catalysts with small size have attracted wide research attention in catalysis but are difficult to synthesize because high-temperature annealing required for alloying inevitably accelerates metal sintering and leads to larger particles. Here, we report a simple and scalable critical interparticle distance method for the synthesis of a family of bimetallic nanocluster catalysts with an average particle size of only 1.5 nm by using large-surface-area carbon black supports at high temperatures, which consist of 12 diverse combinations of 3 noble metals (Pt, Ru, and Rh) and 4 other metals (Cr, Fe, Zr, and Sn). In this strategy, high-temperature treatments ensure the formation of alloyed bimetallic nanoparticles and enlargement of the interparticle distance on high-surface-area supports significantly suppresses metal sintering. The prepared ultrafine Pt2Sn and RuSn nanocluster catalysts exhibited enhanced performance in catalyzing the synthesis of aromatic secondary amines and the selective hydrogenation of furfural, respectively.
Application of organic amine additive in synthesis of fluorescent dye intermediate through olefin hydroformylation reaction
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Paragraph 0015-0023, (2021/07/31)
The invention discloses application of an organic amine additive in synthesis of a fluorescent dye intermediate through olefin hydroformylation reaction, and the application comprises the following steps: S1, the structure of the additive involved in the patent takes a nitrogen atom as a center, and three substituent groups linked with the nitrogen atom are alkyl groups or aromatic groups; and S2, in the hydroformylation reaction process, very few additives are introduced into the reaction system. The activity of a rhodium-aryl phosphine catalyst and the chemical selectivity of a product aldehyde can be obviously improved by using proper types and quantity of additives. The organic amine additive has the characteristics that compared with other types of additives reported in the literature, the organic amine additive can better regulate and control the activity of a rhodium-aryl phosphine catalyst and greatly improve the chemical selectivity of the product aldehyde, the organic amine additive provided by the invention can overcome the defects of other types of additives reported in the literature, and the cost of hydroformylation industrial production of various olefins is reduced.
Intermolecular C-O Bond Formation with Alkoxyl Radicals: Photoredox-Catalyzed α-Alkoxylation of Carbonyl Compounds
Banoun, Camille,Bourdreux, Flavien,Magnier, Emmanuel,Dagousset, Guillaume
supporting information, p. 8926 - 8930 (2021/11/17)
Due to the high reactivity of alkoxyl (RO·) radicals and their propensity to easily undergo β-scission or Hydrogen Atom Transfer (HAT) reactions, intermolecular alkoxylations involving RO· radicals are barely described. We report herein for the first time the efficient intermolecular trapping of alkoxyl radicals by silyl enol ethers. This photoredox-mediated protocol enables the introduction of both structurally simple and more complex alkoxy groups into a wide range of ketones and amides.
Aqueous phase hydrogenation of furfural to tetrahydrofurfuryl alcohol over Pd/UiO-66
Kogan, Victor M.,Liu, Ying-Ya,Sun, Zhichao,Wang, Anjie,Wang, Chunhua,Wang, Yao,Yu, Zhiquan
, (2020/10/09)
A Pd/UiO-66 catalyst was synthesized with well-dispersed Pd nanoparticles. The obtained catalyst was tested in the hydrogenation of furfural to tetrahydrofurfuryl alcohol in various solvents, Water was found to be the most suitable solvent. Pd/UiO-66 exhibited much higher activity than Pd/SiO2 and Pd/γ-Al2O3, completely converting furfural to tetrahydrofurfuryl alcohol with 100% selectivity under mild conditions. The hydrogenation of C[dbnd]O moiety in tetrahydrofurfural was rate-determining step. Static adsorption measurement indicated that the adsorption of furfural on UiO-66 was significantly stronger than that on SiO2 or γ-Al2O3, suggesting that the adsorption play an important role in the gas-liquid-solid furfural hydrogenation reaction.
Selective hydrogenation of furfural to furfuryl alcohol over Pd/TiH2 catalyst
Wang, Zhuangqing,Wang, Xinchao,Zhang, Chao,Arai, Masahiko,Zhou, Leilei,Zhao, Fengyu
, (2021/05/13)
In this work, the selective hydrogenation of furfural to furfuryl alcohol has been studied over Pd/TiH2 catalysts. The catalytic performances of several catalysts with different Pd loading (0.2–3% in weight) were discussed, among which a higher selectivity to furfuryl alcohol was obtained over 0.5Pd/TiH2 and it gave rise to a 73% furfural alcohol selectivity at complete conversion at 60 °C. The physicochemical properties of catalysts were well characterized by TEM, XRD, XPS, Raman, TPR and TPD, as well as in-situ DRIFT for the adsorption of the reactant. The size and the electronic state of Pd particles, and the surface defects of catalysts presented significant influence on the catalytic performance. The furfural is preferentially adsorbed with its C=O bond on the boundary of Pd particle and TiH2 support, leading to the high selectivity to furfuryl alcohol.
Site- And enantiodifferentiating C(sp3)-H oxidation enables asymmetric access to structurally and stereochemically diverse saturated cyclic ethers
Liu, Lei,Sun, Shutao,Yang, Yiying,Zhang, Dongju,Zhao, Ran
supporting information, p. 19346 - 19353 (2020/12/01)
A manganese-catalyzed site- and enantiodifferentiating oxidation of C(sp3)-H bonds in saturated cyclic ethers has been described. The mild and practical method is applicable to a range of tetrahydrofurans, tetrahydropyrans, and medium-sized cyclic ethers with multiple stereocenters and diverse substituent patterns in high efficiency with extremely efficient site- and enantiodiscrimination. Late-stage application in complex biological active molecules was further demonstrated. Mechanistic studies by combined experiments and computations elucidated the reaction mechanism and origins of stereoselectivity. The ability to employ ether substrates as the limiting reagent, together with a broad substrate scope, and a high level of chiral recognition, represent a valuable demonstration of the utility of asymmetric C(sp3)-H oxidation in complex molecule synthesis.
Selective hydrogenation of aromatic furfurals into aliphatic tetrahydrofurfural derivatives
Chen, Bingfeng,Han, Buxing,Li, Shaopeng,Liu, Huizhen,Shen, Xiaojun,Wang, Yanyan,Yang, Youdi
supporting information, p. 4937 - 4942 (2020/11/07)
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
Controllable chemoselective hydrogenation of furfural by PdAg/C bimetallic catalysts under ambient operating conditions: An interesting Ag switch
Wu, Zhi-Lei,Wang, Jian,Wang, Shuo,Zhang, Ya-Xin,Bai, Guo-Yi,Ricardez-Sandoval, Luis,Wang, Gui-Chang,Zhao, Bin
supporting information, p. 1432 - 1442 (2020/03/11)
Hydrogenation of furfural to value-added chemical products is largely hindered by its multiple reaction pathways and complicated product distribution. Thus, to selectively achieve the desired products, catalysts with precise catalytic properties are highly required. Herein, a series of PdAg bimetallic nanoparticles (NPs) of similar size and tunable composition supported on activated carbon (Pd4Ag1/C, Pd2Ag1/C, Pd1Ag1/C and Pd2Ag3/C) were synthesized in a controlled manner and applied in the selective hydrogenation of furfural. Interestingly, an obvious composition-dependent catalytic performance was observed: upon incrementally increasing the proportion of Ag in PdAg NPs, the hydrogenation selectivity can transform from tetrahydrofurfuryl alcohol (sel. 94% for Pd4Ag1/C) to furfuryl alcohol (sel. 95% for Pd1Ag1/C) with nearly complete conversion (99%) of furfural. DFT calculations revealed that the adsorption free energy of in situ generated furfuryl alcohol on Pd(111) surface is inversely proportional correlated with the Ag content in PdAg bimetallic NPs, which accounts for the alteration of chemoselectivity. Importantly, the present study is the first demonstration of composition-induced selectivity reversal for the hydrogenation of furfural under ambient conditions (25 °C, 0.1 MPa H2).
