6344-66-7Relevant academic research and scientific papers
Palladated composite of Cu-BDC MOF and perlite as an efficient catalyst for hydrogenation of nitroarenes
Koohestani, Fatemeh,Sadjadi, Samahe
, (2021/11/04)
A novel composite of metal-organic framework and perlite is prepared through hydrothermal treatment of terephthalic acid and Cu(NO3)2·3H2O in the presence of perlite. The resulting composite was then utilized as a support for the immobilization of Pd nanoparticles. The obtained compound was characterized via XRD, TGA, ICP, FTIR, TEM, FE-SEM/EDS and elemental mapping analysis and applied as a catalyst for the hydrogenation of nitroarenes under mild reaction condition. The results approved that the catalyst could efficiently promote hydrogenation of various nitroarenes with different electronic densities and steric properties. Moreover, the catalyst showed high selectivity towards hydrogenation of nitro groups. Hot filtration test affirmed heterogeneous nature of catalysis. Furthermore, the present catalytic composite was highly recyclable with low Pd leaching. A comparative study also approved superior activity of the composite compared to palladated perlite and metal-organic framework.
Cyclic (Alkyl)(amino)carbene Ligand-Promoted Nitro Deoxygenative Hydroboration with Chromium Catalysis: Scope, Mechanism, and Applications
Zhao, Lixing,Hu, Chenyang,Cong, Xuefeng,Deng, Gongda,Liu, Liu Leo,Luo, Meiming,Zeng, Xiaoming
supporting information, p. 1618 - 1629 (2021/01/25)
Transition metal catalysis that utilizes N-heterocyclic carbenes as noninnocent ligands in promoting transformations has not been well studied. We report here a cyclic (alkyl)(amino)carbene (CAAC) ligand-promoted nitro deoxygenative hydroboration with cost-effective chromium catalysis. Using 1 mol % of CAAC-Cr precatalyst, the addition of HBpin to nitro scaffolds leads to deoxygenation, allowing for the retention of various reducible functionalities and the compatibility of sensitive groups toward hydroboration, thereby providing a mild, chemoselective, and facile strategy to form anilines, as well as heteroaryl and aliphatic amine derivatives, with broad scope and particularly high turnover numbers (up to 1.8 × 106). Mechanistic studies, based on theoretical calculations, indicate that the CAAC ligand plays an important role in promoting polarity reversal of hydride of HBpin; it serves as an H-shuttle to facilitate deoxygenative hydroboration. The preparation of several commercially available pharmaceuticals by means of this strategy highlights its potential application in medicinal chemistry.
Copper-Based Intermetallic Electride Catalyst for Chemoselective Hydrogenation Reactions
Ye, Tian-Nan,Lu, Yangfan,Li, Jiang,Nakao, Takuya,Yang, Hongsheng,Tada, Tomofumi,Kitano, Masaaki,Hosono, Hideo
, p. 17089 - 17097 (2017/12/06)
The development of transition metal intermetallic compounds, in which active sites are incorporated in lattice frameworks, has great potential for modulating the local structure and the electronic properties of active sites, and enhancing the catalytic activity and stability. Here we report that a new copper-based intermetallic electride catalyst, LaCu0.67Si1.33, in which Cu sites activated by anionic electrons with low work function are atomically dispersed in the lattice framework and affords selective hydrogenation of nitroarenes with above 40-times higher turnover frequencies (TOFs up to 5084 h-1) than well-studied metal-loaded catalysts. Kinetic analysis utilizing isotope effect reveals that the cleavage of the H-H bond is the rate-determining step. Surprisingly, the high carrier density and low work function (LWF) properties of LaCu0.67Si1.33 enable the activation of hydrogen molecules with extreme low activation energy (Ea = 14.8 kJ·mol-1). Furthermore, preferential adsorption of nitroarenes via a nitro group is achieved by high oxygen affinity of LaCu0.67Si1.33 surface, resulting in high chemoselectivity. The present efficient catalyst can further trigger the hydrogenation of other oxygen-containing functional groups such as aldehydes and ketones with high activities. These findings demonstrate that the transition metals incorporated in the specific lattice site function as catalytically active centers and surpass the conventional metal-loaded catalysts in activity and stability.
FePd alloy nanoparticles assembled on reduced graphene oxide as a catalyst for selective transfer hydrogenation of nitroarenes to anilines using ammonia borane as a hydrogen source
Metin, ?nder,Mendoza-Garcia, Adriana,Dalmizrak, Di?dem,Gültekin, Mehmet Serdar,Sun, Shouheng
, p. 6137 - 6143 (2016/08/05)
Addressed herein is a facile protocol for the synthesis and assembly of FePd alloy nanoparticles (NPs) on reduced graphene oxide (rGO) to catalyze transfer hydrogenation of nitroarenes to anilines under ambient conditions. 3.5 nm FePd NPs were synthesized by using a surfactant-assisted co-reduction method that allowed NP composition control. FePd NPs were then assembled on rGO via a liquid-phase self-assembly method and studied as catalysts to promote hydrogen transfer from ammonia borane (AB) to numerous nitroarenes in aqueous methanol solutions at room temperature. Among three different rGO-FePd, the commercial C-Pd and rGO-Pd catalysts tested, rGO-Fe48Pd52 showed the highest efficiency in converting nitroarenes to anilines, achieving >90% yields within 10-20 min of reactions. Our work demonstrates an efficient and selective approach to transfer hydrogenation of nitroarenes to anilines.
Recyclable aluminium oxy-hydroxide supported Pd nanoparticles for selective hydrogenation of nitro compounds via sodium borohydride hydrolysis
G?ksu, Haydar
, p. 8498 - 8504 (2015/11/10)
The reduction of aromatic/aliphatic nitro compounds to primary amines with high yields was easily realized by transfer hydrogenation comprising commercially available aluminium oxy-hydroxide-supported Pd nanoparticles (0.5 wt% Pd, Pd/AlO(OH)) as catalysts and NaBH4 as the hydrogen reservoir at room temperature in a water/methanol mixture (v/v = 7/3). The presented catalytic methodology is highly efficient for the reduction of various nitro compounds as well as reusable. A variety of R-NO2 derivatives were tested by performing the Pd/AlO(OH) catalysed reduction reaction and all the nitro compounds were selectively reduced to their corresponding primary amines in reaction times ranging from 0.75 to 13 min with yields reaching up to 99%. This process can be assessed as an eco-friendly method involving both reusable catalysts (Pd/AlO(OH) NPs) and hydrogen sources (NaBH4).
A Mild and Chemoselective Reduction of Nitro and Azo Compounds Catalyzed by a Well-Defined Mo3S4 Cluster Bearing Diamine Ligands
Pedrajas, Elena,Sorribes, Iván,Junge, Kathrin,Beller, Matthias,Llusar, Rosa
, p. 2675 - 2681 (2015/09/15)
Herein, we report a novel well-defined diamino Mo3S4-based catalyst system for the reduction of nitroarenes and azo compounds to the corresponding anilines with silanes as reducing agents. This catalytic protocol provides a facile route to access aromatic amines under mild conditions in good to excellent yields. Notably, even anilines functionalized with other potentially reducible moieties are obtained with high selectivity. The new chemoselective catalyst of formula [Mo3S4Cl3(dmen)3](BF4) (dmen: N,N′-dimethylethylenediamine) is conveniently synthesized through coordination of the diamine ligand to the incomplete Mo3S4 cubane-type cluster core in a one-pot two-step procedure. The crystal structure of the [Mo3S4Cl3(dmen)3]+ cation confirms the formation of a single isomer in which the chlorine atom lies trans to the bridging sulfur atom to afford a C3 symmetry complex with intrinsic backbone chirality. The structure is preserved in solution, as evidenced by multinuclear NMR spectroscopy and electrospray-ionization mass spectrometric techniques.
Tandem dehydrogenation of ammonia borane and hydrogenation of nitro/nitrile compounds catalyzed by graphene-supported NiPd alloy nanoparticles
Goeksu, Haydar,Ho, Sally Fae,Metin, Oender,Korkmaz, Katip,Mendoza Garcia, Adriana,Gueltekin, Mehmet Serdar,Sun, Shouheng
, p. 1777 - 1782 (2014/06/24)
We report a facile synthesis of monodisperse NiPd alloy nanoparticles (NPs) and their assembly on graphene (G) to catalyze the tandem dehydrogenation of ammonia borane (AB) and hydrogenation of R-NO2 and/or R-CN to R-NH2 in aqueous methanol solutions at room temperature. The 3.4 nm NiPd alloy NPs were prepared by coreduction of nickel(II) acetate and palladium(II) acetlyacetonate by borane-tert-butylamine in oleylamine and deposition on G via a solution phase self-assembly process. G-NiPd showed composition-dependent catalysis on the tandem reaction with G-Ni 30Pd70 being the most active. A variety of R-NO 2 and/or R-CN derivatives were reduced selectively into R-NH 2 via G-Ni30Pd70 catalyzed tandem reaction in 5-30 min reaction time with the conversion yields reaching up to 100%. Our study demonstrates a new approach to G-NiPd-catalyzed dehydrogenation of AB and hydrogenation of R-NO2 and R-CN. The G-NiPd NP catalyst is efficient and reusable, and the reaction can be performed in an environment-friendly process with short reaction times and high yields.
Chemoselective transfer hydrogenation to nitroarenes mediated by cubane-type Mo3S4 cluster catalysts
Sorribes, Iván,Wienh?fer, Gerrit,Vicent, Cristian,Junge, Kathrin,Llusar, Rosa,Beller, Matthias
experimental part, p. 7794 - 7798 (2012/10/08)
Chemoselective cubes: Cubane-type [Mo3S4X 3(dmpe)3]+ clusters (dmpe=1,2-(bis) dimethylphosphinoethane), in combination with an azeotropic 5:2 mixture of HCOOH and NEt3 as the reducing agent, act as selective cluster catalysts (X=H) or precatalysts (X=Cl) for the transfer hydrogenation of functionalized nitroarenes, without the formation of hazardous hydroxylamines. Copyright
