98-00-0Relevant academic research and scientific papers
Manganese-Catalyzed Hydrogenation of Sclareolide to Ambradiol
Zubar, Viktoriia,Lichtenberger, Niels,Schelwies, Mathias,Oeser, Thomas,Hashmi, A. Stephen K.,Schaub, Thomas
, (2021/11/16)
The hydrogenation of (+)-Sclareolide to (?)-ambradiol catalyzed by a manganese pincer complex is reported. The hydrogenation reaction is performed with an air- and moisture-stable manganese catalyst and proceeds under relatively mild reaction conditions at low manganese and base loadings. A range of other esters could be successfully hydrogenated leading to the corresponding alcohols in good to quantitative yields using this easy-to-make catalyst. A scale-up experiment was performed leading to 99.3 % of the isolated yield of (?)-Ambradiol.
Highly effective and chemoselective hydrodeoxygenation of aromatic alcohols
Han, Buxing,He, Mingyuan,Mei, Xuelei,Wu, Haihong,Wu, Wei,Xu, Caiyun,Zhai, Jianxin,Zhang, Kaili,Zhang, Zhanrong,Zheng, Bingxiao
, p. 1629 - 1635 (2022/02/21)
Effective hydrodeoxygenation (HDO) of aromatic alcohols is very attractive in both conventional organic synthesis and upgrading of biomass-derived molecules, but the selectivity of this reaction is usually low because of the competitive hydrogenation of the unsaturated aromatic ring and the hydroxyl group. The high activity of noble metal-based catalysts often leads to undesired side reactions (e.g., saturation of the aromatic ring) and excessive hydrogen consumption. Non-noble metal-based catalysts suffer from unsatisfied activity and selectivity and often require harsh reaction conditions. Herein, for the first time, we report chemoselective HDO of various aromatic alcohols with excellent selectivity, using porous carbon-nitrogen hybrid material-supported Co catalysts. The C-OH bonds were selectively cleaved while leaving the aromatic moiety intact, and in most cases the yields of targeted compounds reached above 99% and the catalyst could be readily recycled. Nitrogen doping on the carbon skeleton of the catalyst support (C-N matrix) significantly improved the yield of the targeted product. The presence of large pores and a high surface area also improved the catalyst efficiency. This work opens the way for efficient and selective HDO reactions of aromatic alcohols using non-noble metal catalysts.
Platinum thiolate complexes supported by PBP and POCOP pincer ligands as efficient catalysts for the hydrosilylation of carbonyl compounds
Chang, Jiarui,Chen, Xuenian,Xue, Man-Man,Zhang, Jie
supporting information, p. 2304 - 2312 (2022/02/21)
Diphosphino-boryl-based PBP pincer platinum thiolate complexes, [Pt(SR){B(NCH2PtBu2)2-1,2-C6H4}] (R = H, 1a; Ph, 1b), and benzene-based bisphosphinite POCOP pincer platinum thiolate complexes, [Pt(SR)(tBu2PO)2-1,3-C6H3] (R = H, 2a; Ph, 2b), were prepared
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.
Solvent effect on the rate and direction of furfural transformations during hydrogenation over the Pd/C catalyst
Belskaya, O. B.,Likholobov, V. A.,Mironenko, R. M.
, p. 64 - 69 (2022/02/25)
The rate and directions of transformations during the liquid-phase hydrogenation of furfural with molecular hydrogen in the presence of the 5%Pd/C catalyst (at 423 K, 3 MPa) depend substantially on the chemical nature of the solvent. The main products of
Comparative account of catalytic activity of Ru- and Ni-based nanocomposites towards reductive amination of biomass derived molecules
Bhanage, Bhalchandra M.,Gokhale, Tejas A.,Raut, Amol B.
, (2021/06/18)
This work includes an effective comparison of metallic ruthenium and nickel nanoparticles loaded on montmorillonite clay (MMT) for reductive amination reaction of biomass-derived molecules. It comprises an eco-friendly reaction using water as a solvent, utilizing molecular hydrogen and liquor ammonia (25% aq. solution) for the synthesis of primary amines from bio-derived aldehydes within 3–10 h of reaction time. Various parameters such as temperature, hydrogen pressure, substrate/ammonia concentration ratio, and reaction time were optimized while comparing the selectivity of primary amines for both catalysts. The applicability scope of these catalysts was explored with a library of aryl and heterocyclic aldehydes. The reductive amination of crude furfural extracted from biomass feedstock (rice husk) and pure xylose sugar was tested, showing yields in the range of 11–36%, to show the wider industrial scope of both nanocomposites. Gram scale conversion was also carried out to showcase the bulk scalability of the Ru/MMT catalyst.
Self-regulated catalysis for the selective synthesis of primary amines from carbonyl compounds
Fan, Xiaomeng,Gao, Jin,Gao, Mingxia,Jia, Xiuquan,Ma, Jiping,Xu, Jie
supporting information, p. 7115 - 7121 (2021/09/28)
Most current processes for the general synthesis of primary amines by reductive amination are performed with enormously excessive amounts of hazardous ammonia. It remains unclear how catalysts should be designed to regulate amination reaction dynamics at a low ammonia-to-substrate ratio for the quantitative synthesis of primary amines from the corresponding carbonyl compounds. Herein we show a facile control of the reaction selectivity in the layered boron nitride supported ruthenium catalyzed reductive amination reaction. Specifically, locating ruthenium to the edge surface of layered boron nitride leads to an increased hydrogenation activity owing to the enhanced interfacial electronic effects between ruthenium and the edge surface of boron nitride. This enables self-accelerated reductive amination reactions which quantitatively synthesize structurally diverse primary amines by reductive amination of carbonyl compounds with twofold ammonia. This journal is
One-pot self-assembly synthesis of Ni-doped ordered mesoporous carbon for quantitative hydrogenation of furfural to furfuryl alcohol
Tang, Yiwei,Qiu, Mo,Yang, Jirui,Shen, Feng,Wang, Xiaoqi,Qi, Xinhua
, p. 1861 - 1870 (2021/03/09)
Ni-Doped ordered mesoporous carbon (Ni@OMC) was prepared by a one-pot solvent evaporation-induced self-assembly (EISA) process with sustainable biomass-derived gallic acid as the carbon precursor, F127 as the soft template and Ni2+as the cross-linker and catalytically active ingredient. Ni particles withca.7.8 nm diameter were uniformly dispersed in the carbon skeleton of the synthesized OMC due to the confinement effects of Ni particles in the carbon skeleton of OMC by coordination between gallic acid molecules and metal Ni2+ions in the EISA process. The as-synthesized Ni@OMC sample showed excellent catalytic performance for the hydrogenation of biomass-derived furfural into furfuryl alcohol (FFA), and a FFA yield as high as 98% could be achieved at 180 °C in 4 h reaction time in 1-propanol solvent in the presence of 3 MPa H2pressure. The prepared Ni@OMC exhibited good stability and recyclability. This work provides a green and simple one-pot strategy for the synthesis of metal-doped OMCs without using harmful phenolic and formaldehyde compounds, which should have many applications in fields such as catalysis, drug delivery and energy storage.
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.
