Stereoselective single (copper) or double (platinum) boronation of alkynes catalyzed by magnesia-supported copper oxide or platinum nanoparticles

Copper(II) oxide nanoparticles supported on magnesia have been prepared from Cu(II) supported on magnesia by hydrogen reduction at 400 °C followed by storage under ambient conditions. X-ray photoelectron spectroscopy of the material clearly shows that immediately after the reduction copper(0)-metal nanoparticles are present on the magnesia support, but they undergo fast oxidation to copper oxide upon contact with the ambient for a short time. TEM images show that the catalytically active CuO/MgO material is formed of well-dispersed copper oxide nanoparticles supported on fibrous MgO. CuO/MgO exhibits a remarkable catalytic activity for the monoborylation of aromatic, aliphatic, terminal, and internal alkynes, the products being formed with high regio- (borylation at the less substituted carbon) and stereoselectivity (trans-configured). CuO/MgO exhibits complete chemoselectivity towards the monoborylation of alkynes in the presence of alkenes. Other metal nanoparticles such as gold or palladium are inactive towards borylation, but undergo undesirable oligomerization or partial hydrogenation of the C≡C triple bond. In contrast, platinum, either supported on magnesia or on nanoparticulate ceria, efficiently promotes the stereoselective diborylation of alkynes to yield a cis-configured diboronate alkene. By using platinum as the catalyst we have developed a tandem diborylation/hydrogenation reaction that gives vic-diboronated alkanes from alkynes in one pot.     

Synergism of Pt nanoparticles and iron oxide support for chemoselective hydrogenation of nitroarenes under mild conditions

An efficient and low-cost supported Pt catalyst for hydrogenation of niroarenes was prepared with colloid Pt precursors and α-Fe₂O₃ as a support. The catalyst with Pt content as low as 0.2 wt% exhibits high activities, chemoselectivities and stability in the hydrogenation of nitrobenzene and a variety of niroarenes. The conversion of nitrobenzene can reach 3170 mol_conv h^?1 mol_Pt^?1 under mild conditions (30 °C, 5 bar), which is much higher than that of commercial Pt/C catalyst and many reported catalysts under similar reaction conditions. The spatial separation of the active sites for H₂ dissociation and hydrogenation should be responsible for the high chemoselectivity, which decreases the contact possibility between the reducible groups of nitroarenes and Pt nanoparticles. The unique surface properties of α-Fe₂O₃ play an important role in the reaction process. It provides active sites for hydrogen spillover and reactant adsorption, and ultimately completes the hydrogenation of the nitro group on the catalyst surface.     

Ambient-pressure hydrogenation of ketones and aldehydes by a metal-ligand bifunctional catalyst [Cp*Ir(2,2′-bpyO)(H2O)] without using base

An efficient catalytic system for hydrogenation of ketones and aldehydes using a Cp*Ir complex [Cp*Ir(2,2′-bpyO)(H₂O)] bearing a bipyridine-based functional ligand as catalyst has been developed. A wide variety of secondary and primary alcohols were synthesized by the catalyzed hydrogenation of ketones and aldehydes under facile atmospheric-pressure without a base. The catalyst also displays an excellent chemoselectivity towards other carbonyl functionalities and unsaturated motifs. This catalytic system exhibits high activity for hydrogenation of ketones and aldehydes with H₂ gas.     

Raney Ni催化二亚糠基丙酮加氢制取长链烷烃前驱体的特性研究

采用Raney Ni为催化剂,考察了反应温度、压力、时间和溶剂对二亚糠基丙酮加氢制取长链烷烃前驱体催化性能的影响。结果表明,Raney Ni对二亚糠基丙酮具有很好的低温加氢性能,升高反应温度和压力均有利于加氢反应的进行,但过高的温度反而不利于加氢反应。在50℃和2.5 MPa下反应2 h,二亚糠基丙酮转化率达99.5%以上,饱和加氢产物的总选择性达到80.8%。此外,加氢中间产物的变化结果表明,二亚糠基丙酮的双键加氢容易程度为,烯键>呋喃环双键>C=O双键。Raney Ni 在甲醇溶剂中的加氢性能明显高于在四氢呋喃、环己烷或水溶剂中的加氢性能。     

Chemoselective hydrogenation of α,β-unsaturated aldehydes with modified Pd/C catalyst

Selective hydrogenation of α, β-unsaturated aldehydes with modified Pd/C catalyst was developed.The reduction of C=O bond could be efficiently inhibited by the addition of carbonates,and high selectivity to the corresponding saturated aldehydes was achieved under mild conditions.This protocol provides an alternative for efficient preparation of saturated aldehydes.     

Highly Active Supported Pt Nanocatalysts Synthesized by Alcohol Reduction towards Hydrogenation of Cinnamaldehyde: Synergy of Metal Valence and Hydroxyl Groups

The hydrogenation of α,β‐unsaturated aldehydes to allylic alcohols or saturated aldehydes provides a typical example to study the catalytic effect on structure‐sensitive reactions. In this work, supported platinum nanocatalysts over hydrotalcite were synthesized by an alcohol reduction method. The Pt catalyst prepared by the reduction with a polyol (ethylene glycol) outperforms those prepared with ethanol and methanol in the hydrogenation of cinnamaldehyde. The selectivity towards the C=O bond is the highest over the former, although its mean size of Pt particles is the smallest. The hydroxyl groups on hydrotalcite could act as an internally accessible promoter to enhance the selectivity towards the C=O bond. The optimal Pt catalyst showed a high activity with an initial turnover frequency (TOF) of 2.314 s^?1. This work unveils the synergic effect of metal valence and in situ promoter on the chemoselective hydrogenation, which could open up a new direction in designing hydrogenation catalysts.     

水溶性钯配合物催化柠檬醛的选择加氢反应研究 Ⅰ.反应条件的影响

研究了在水／有机物两相体系中水溶性钯－膦配合物催化柠檬醛的加氢反应．考察了反应温度、氢气压力、底物和催化剂浓度、反应时间、水相ｐＨ值等对该反应的影响，并与几种柠檬醛衍生物的加氢结果进行了比较．发现仅用蒸馏水作水相，则主要产物是二氢香茅醛（＞９３％）；而水相中加入Ｎａ２ＣＯ３后，则主要产物为香茅醛（９７％），且加氢速度比同样条件下使用Ｐｄ／Ｃ催化剂快得多．     

PRODUCTION OF LIGHT OLEFINS FROM CO2 HYDROGENATION OVER Fe/SILICALITE-2 CATALYST IV. PERFORMANCE OF THE K-Fe-MnO/Si-2 CATALYST

A new K-Fe-MnO/Si-2 catalyst has been developed for CO2 hydrogenation, which exhibits a fascinating reaction activity and light olefin selectivity for CO2 hydrogenation. Over the catalyst, it is observed that olefin selectivity increases apparently with reaction temperature and/or GHSV, while decreases when reaction pressure is up. Furthermore, the catalyst exhibits a better stability for CO2 hydrogenation. However, coke deposited on catalyst surface is formed at the beginning of the reaction period and then reached a stable state during CO2 hydrogenation. Generally, the K-Fe-MnO/Si-2 catalyst can be regenerated for CO2 hydrogenation, the same selectivity of C2=-C4=alkenes is regained without any decrease in catalyst activity with time on stream.     

Primary Amines by Transfer Hydrogenative Reductive Amination of Ketones by Using Cyclometalated IrIII Catalysts

Cyclometalated iridium complexes are found to be versatile catalysts for the direct reductive amination (DRA) of carbonyls to give primary amines under transfer‐hydrogenation conditions with ammonium formate as both the nitrogen and hydrogen source. These complexes are easy to synthesise and their ligands can be easily tuned. The activity and chemoselectivity of the catalyst towards primary amines is excellent, with a substrate to catalyst ratio (S/C) of 1000 being feasible. Both aromatic and aliphatic primary amines were obtained in high yields. Moreover, a first example of homogeneously catalysed transfer‐hydrogenative DRA has been realised for β‐keto ethers, leading to the corresponding β‐amino ethers. In addition, non‐natural α‐amino acids could also be obtained in excellent yields with this method.     

Highly chemoselective hydrogenation with retention of the epoxide function using a heterogeneous Pd/C-ethylenediamine catalyst and THF

In general, palladium-carbon (Pd/C) catalyzed hydrogenation of epoxides affords the corresponding primary and secondary alcohols as a mixture. It has been found that the catalytic activity of a Pd/C -ethylenediamine complex catalyst [Pd/C(en)] in the hydrogenolysis of epoxide functions is drastically reduced. Herein we describe a mild and chemoselective method for the hydrogenation of olefin, nitro, and azide functions with retention of the epoxide function. The chemoselectivity was accomplished by using a combination of 5% Pd/C(en) and THF as solvent. A significant drop in the chemoselectivity of the hydrogenation is observed with 5% Pd/C(en) in MeOH. These results reinforce the utility of epoxides as important precursors of alcohols in synthetic chemistry.     

Effect of transition metals (Cr, Mn, Fe, Co, Ni and Cu) on selective hydrogenation of cinnamaldehyde over Pt/CNTs catalyst

Summary The effect of transition metals (Cr, Mn, Fe, Co, Ni and Cu) on the selective hydrogenation of cinnamaldehyde (CMA) to the corresponding semi-hydrogenated product over Pt/CNTs catalyst has been studied in ethanol at 343 K under 2.0 MPa H₂ pressure. PtNi/CNTs catalyst shows good catalytic activity and selectivity of C=C bond hydrogenation, 68.4% for conversion of CMA and 97.0% for selectivity of hydrocinnamaldehyde (HCMA). PtCo/CNTs catalyst shows good catalytic activity and selectivity of C=O bond hydrogenation, 91.3% for conversion of CMA and 88.2% for selectivity of cinnamylalcohol (CMO).     

氮掺杂碳包覆纳米钴颗粒用于硝基芳烃室温选择性加氢（英文）

通过硝基芳烃选择性加氢能高效地制备芳香胺和环胺,其中芳香胺作为重要的化工中间体应用于多个领域(精细化工、商业产品和聚合物).在加氢反应过程中,硝基的还原伴随着生成一些副产物(如亚硝基和偶氮化合物).同时对于含还原性基团的取代硝基苯,硝基的选择还原也面临着很大的挑战.金属钴是常用的硝基加氢催化剂活性成分,但是由于对反应底物的过度吸附,导致其选择性不高.早期研究发现,氮掺杂碳催化剂能有效吸附硝基基团,从而在硝基苯加氢中表现出一定活性,但对分子氢的活化不足.因此,氮掺杂碳作为吸附材料与钴构建复合催化剂,能够发挥吸附和活化氢的协同作用,从而高效催化硝基苯加氢.基于此,本课题组发展了一种制备方法,可将钴颗粒尺寸限制在10 nm左右,且包覆在氮掺杂碳中,并应用于对硝基苯酚的室温选择性加氢反应中,发现相较于碳负载钴和氮掺杂碳催化剂,所制催化剂在室温下表现出了很好的活性和选择性.在此基础上,本文采用元素分析、X射线光电子能谱(XPS)和拉曼光谱(Raman)等手段对催化剂形貌和结构进行了研究.表征结果表明,保持钴前驱体的量不变,随着氮化碳加入量的增加,催化剂中氮掺杂浓度提高;当氮化碳/钴1时,氮掺杂浓度不变.红外结果表明,与普通碳载体相比,氮掺杂碳对硝基苯有很强的吸附作用,而氮掺杂碳包覆的钴催化剂也表现出同样的结果.通过调节氮的掺杂浓度,一方面可以修饰碳载体的电子结构,增加表面缺陷的浓度,提高与反应底物的相互作用;另一方面可以促进电子由钴颗粒转移至与之相连的氮原子上,因此进一步促进钴颗粒对分子氢的活化作用.该复合结构的催化剂实现了底物吸附和氢活化的协同作用,氮掺杂碳将反应底物吸附在表面,钴颗粒活化氢,随后解离的氢原子与表面吸附物反应,从而实现硝基苯的高效加氢.其中Co@NC-1催化活性最高,并在循环套用10次后,仍维持较高的催化活性,同时对含其它取代基的硝基苯均表现很高的活性和选择性.     

Electrocatalytically Activating and Reducing N2 Molecule by Tuning Activity of Local Hydrogen Radical

Decarbonizing N₂ conversion is particularly challenging, but essential for sustainable development of industry and agriculture. Herein, we achieve electrocatalytic activation/reduction of N₂ on X/Fe−N−C (X=Pd, Ir and Pt) dual-atom catalysts under ambient condition. We provide solid experimental evidence that local hydrogen radical (H*) generated on the X site of the X/Fe−N−C catalysts can participate in the activation/reduction of N₂ adsorbed on the Fe site. More importantly, we reveal that the reactivity of X/Fe−N−C catalysts for N₂ activation/reduction can be well adjusted by the activity of H* generated on the X site, i.e., the interaction between the X−H bond. Specifically, X/Fe−N−C catalyst with the weakest X−H bonding exhibits the highest H* activity, which is beneficial to the subsequent cleavage of X−H bond for N₂ hydrogenation. With the most active H*, the Pd/Fe dual-atom site promotes the turnover frequency of N₂ reduction by up to 10 times compared with the pristine Fe site.     

Fast Reductive Amination by Transfer Hydrogenation “on Water”

Reductive amination of various ketones and aldehydes by transfer hydrogenation under aqueous conditions has been developed, by using cyclometallated iridium complexes as catalysts and formate as hydrogen source. The pH value of the solution is shown to be critical for a high catalytic chemoselectivity and activity, with the best pH value being 4.8. In comparison with that in organic solvents, the reductive amination in an aqueous phase is faster, and the molar ratio of the substrate to the catalyst (S/C) can be set as high as 1×10⁵, the highest S/C value ever reported in reductive amination reactions. The catalyst is easy to access and the reaction is operationally simple, allowing a wide range of ketones and aldehydes to react with various amines in high yields. The protocol provides a practical and environmental friendly new method for the synthesis of amine compounds.     

Effect of Transition Metals on Selective Hydrogenation of Cinnamaldehyde over Pt／ZrO2 Catalysts

The effect of transition metals (Cr, Mn, Fe, Co and Ni) on the hydrogenation of cinnamaldehyde over Pt/ZrO2 catalysts was studied in ethanol at 343K under 2.0MPa H2 pressure. PtCo/ZrO2 and PtFe/ZrO2 catalysts exhibit high selectivity and activity of hydrogenation for C=O (93.8% at 87.3% conversion and 83.6% at 88.6% conversion, respectively), and PtNi/ZrO2 exhibits high selectivity of hydrogenation for C=C (64.3% at 70.6% conversion). In the presence of trace H2O and NaOH, over the PtNi/ZrO2 (0.4wt%Ni) catalyst the selectivity to hydrocinnamalde hydereaches 90.6% and the conversion of cinnamaldehyde is 90.5%.     

Temperature dependence of benzene hydrogenation over sulfide catalysts

Non-Arrhenius temperature dependence of benzene hydrogenation was found for sulfide alumina-supported (Ni,Mo) and (Ni,W) catalysts under unsteady-state reaction conditions. It was shown that THE observed decrease in the catalyst activity at high temperature cannot be explained by the increasing role of the reverse reaction. The activity decrease was supposed to result from the catalyst reduction with the reaction mixture.     

Ruthenium-catalyzed intramolecular cyclization of diazo-β-ketoanilides for the synthesis of 3-alkylideneoxindoles

With [Ru(p-cymene)Cl(2)](2) as catalyst, diazo-β-ketoanilides would undergo intramolecular carbenoid arene C-H bond functionalization to afford 3-alkylideneoxindoles in up to 92% yields. The reaction occurs under mild conditions and exhibits excellent chemoselectivity. The lack of primary KIE (k(H)/k(D) ~ 1) suggests that the reaction should not proceed by rate-limiting C-H bond cleavage; a mechanism involving cyclopropanation of the arene is proposed.     

On the Functional Group Tolerance of Ester Hydrogenation and Polyester Depolymerisation Catalysed by Ruthenium Complexes of Tridentate Aminophosphine Ligands

The synthesis of a range of phosphine‐diamine, phosphine‐amino‐alcohol, and phosphine‐amino‐amide ligands and their ruthenium(II) complexes are reported. Five of these were characterised by X‐ray crystallography. The activities of this collection of catalysts were initially compared for the hydrogenation of two model ester hydrogenations. Catalyst turnover frequencies up to 2400 h^?1 were observed at 85 °C. However, turnover is slow at near ambient temperatures. By using a phosphine‐diamine Ru^II complex, identified as the most active catalyst, a range of aromatic esters were reduced in high yield. The hydrogenation of alkene‐, diene‐, and alkyne‐functionalised esters was also studied. Substrates with a remote, but reactive terminal alkene substituent could be reduced chemoselectively in the presence of 4‐dimethylaminopyridine (DMAP) co‐catalyst. The chemoselective reduction of the ester function in conjugated dienoate ethyl sorbate could deliver (2E,4E)‐hexa‐2,4‐dien‐1‐ol, a precursor to leaf alcohol. The monounsaturated alcohol (E)‐hex‐4‐en‐1‐ol was produced with reasonable selectivity, but complete chemoselectivity of C?O over the diene is elusive. High chemoselectivity for the reduction of an ester over an alkyne group was observed in the hydrogenation of an alkynoate for the first time. The catalysts were also active in the depolymerisation reduction of samples of waste poly(ethylene terephthalate) (PET) to produce benzene dimethanol. These depolymerisations were found to be poisoned by the ethylene glycol side product, although good yields could still be achieved.     

酸处理再生NiB非晶态合金催化剂

近年来,非晶态合金由于在催化加氢反应中表现出优良的催化活性和选择性而受到广泛关注[1,2].其中,化学还原法制备的超细N iB非晶态合金具有很高的催化活性,但该类催化剂易于晶化和氧化失活,限制了其工业应用[3,4].因此,提高N iB非晶态合金的稳定性和抗氧化性引起广泛关注.目前,     

Rh基催化剂上CO加氢制C2含氧化物的原位红外光谱研究

 用原位红外光谱考察了Rh-Mn-Li-Fe/SiO2和Rh/SiO2催化剂表面上CO的吸附态及CO加氢反应过程中吸附物种的变化. 结果表明,CO在Rh/SiO2催化剂上仅有线式吸附态存在,而CO在Rh-Mn-Li-Fe/SiO2催化剂上既有线式吸附态存在,又有孪生吸附态存在. 这说明Rh-Mn-Li-Fe/SiO2催化剂中Rh的分散度较高. 经CO加氢反应(3.0 MPa,593 K)后,在Rh-Mn-Li-Fe/SiO2催化剂上可观测到C2含氧化物前驱物种的吸收谱带,而在Rh/SiO2催化剂上未观测到相应的谱带; CO在这两种催化剂上主要以线式吸附态存在,孪生吸附态基本消失. 结合催化剂对CO加氢的催化性能,可以认为线式吸附的CO对生成C2含氧化物有贡献. Rh-Mn-Li-Fe/SiO2催化剂的高活性是由于助剂的存在削弱了其表面吸附CO的 C-O键,促进了CO的活化,从而有利于C2含氧化物前驱物的生成.