5192-03-0Relevant articles and documents
Chemoselective transfer hydrogenation to nitroarenes mediated by oxygen-implanted MoS2
Zhang, Chaofeng,Wang, Xu,Li, Mingrun,Zhang, Zhixin,Wang, Yehong,Si, Rui,Wang, Feng
, p. 1569 - 1577 (2016)
We present an efficient approach for the chemoselective synthesis of arylamines from nitroarenes and formate over an oxygen-implanted MoS2 catalyst (O-MoS2). O-MoS2 was prepared by incomplete sulfidation and reduction of an ammonium molybdate precursor. A number of Mo–O bonds were implanted in the as-synthesized ultrathin O-MoS2 nanosheets. As a consequence of the different coordination geometries of O (MoO2) and S (MoS2), and lengths of the Mo–O and Mo–S bonds, the implanted Mo–O bonds induced obvious defects and more coordinatively unsaturated (CUS) Mo sites in O-MoS2, as confirmed by X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy, high resolution transmission electron microscopy, and extended X-ray absorption fine structure characterization of various MoS2-based materials. O-MoS2 with abundant CUS Mo sites was found to efficiently catalyze the chemoselective reduction of nitroarenes to arylamines.
Aluminum Metal-Organic Framework-Ligated Single-Site Nickel(II)-Hydride for Heterogeneous Chemoselective Catalysis
Antil, Neha,Kumar, Ajay,Akhtar, Naved,Newar, Rajashree,Begum, Wahida,Dwivedi, Ashutosh,Manna, Kuntal
, p. 3943 - 3957 (2021/04/12)
The development of chemoselective and heterogeneous earth-abundant metal catalysts is essential for environmentally friendly chemical synthesis. We report a highly efficient, chemoselective, and reusable single-site nickel(II) hydride catalyst based on robust and porous aluminum metal-organic frameworks (MOFs) (DUT-5) for hydrogenation of nitro and nitrile compounds to the corresponding amines and hydrogenolysis of aryl ethers under mild conditions. The nickel-hydride catalyst was prepared by the metalation of aluminum hydroxide secondary building units (SBUs) of DUT-5 having the formula of Al(μ2-OH)(bpdc) (bpdc = 4,4′-biphenyldicarboxylate) with NiBr2 followed by a reaction with NaEt3BH. DUT-5-NiH has a broad substrate scope with excellent functional group tolerance in the hydrogenation of aromatic and aliphatic nitro and nitrile compounds under 1 bar H2 and could be recycled and reused at least 10 times. By changing the reaction conditions of the hydrogenation of nitriles, symmetric or unsymmetric secondary amines were also afforded selectively. The experimental and computational studies suggested reversible nitrile coordination to nickel followed by 1,2-insertion of coordinated nitrile into the nickel-hydride bond occurring in the turnover-limiting step. In addition, DUT-5-NiH is also an active catalyst for chemoselective hydrogenolysis of carbon-oxygen bonds in aryl ethers to afford hydrocarbons under atmospheric hydrogen in the absence of any base, which is important for the generation of fuels from biomass. This work highlights the potential of MOF-based single-site earth-abundant metal catalysts for practical and eco-friendly production of chemical feedstocks and biofuels.
A novel water-dispersible and magnetically recyclable nickel nanoparticles for the one-pot reduction-Schiff base condensation of nitroarenes in pure water
Ghamari Kargar, Pouya,Ravanjamjah, Asiye,Bagherzade, Ghodsieh
, p. 1916 - 1933 (2021/07/10)
In this work, a heterogeneous nanocatalyst called Ni-Fe3O4@Pectin~PPA ~ Piconal was first synthesized, which was investigated as a bifunctional catalyst containing nickel functional groups. On the other hand, this Ni-Fe3O4@Pectin~PPA ~ Piconal catalyst in aqueous solvents shows a very effective performance at ambient temperature for the nitroarene reduction reaction with sodium borohydride, for which NaBH4 is considered as a reducing agent. This is a novelty magnetic catalyst that was approved by various methods, including Fourier-transform infrared spectroscopy (FT-IR), X-ray powder diffraction (XRD), Dynamic light scattering (DLS), Transmission electron microscopy (TEM), vibrating sample magnetometer (VSM), Inductively coupled plasma (ICP), Energy-dispersive X-ray spectroscopy (EDX), and Field emission scanning electron microscopy (FESEM) analyses. From the satisfactory results obtained from the reduction of nitrogen, this catalytic system is used for a one-pot protocol containing a reduction-Schiff base concentration of diverse nitroarenes. It was corroborated with the heterogeneous catalytic experiments on the one-pot tandem synthesis of imines from nitroarenes and aldehydes. Finally, the novel Ni-Fe3O4@Pectin~PPA ~ Piconal catalyst could function as a more economically desirable and environmentally amicable in the catalysis field. The favorable products are acquired in good to high performance in the attendance of Ni-Fe3O4@Pectin~PPA ~ Piconal as a bifunctional catalyst. This catalyst can be recycled up to six steps without losing a sharp drop.
Calculated oxidation potentials predict reactivity in Baeyer-Mills reactions
Gingrich, Phillip W.,Olson, David E.,Tantillo, Dean J.,Tombari, Robert J.,Tuck, Jeremy R.,Yardeny, Noah
supporting information, p. 7575 - 7580 (2021/09/22)
Azobenzenes are widely used as dyes and photochromic compounds, with the Baeyer-Mills reaction serving as the most common method for their preparation. This transformation is often plagued by low yields due to the formation of undesired azoxybenzene. Here, we explore electronic effects dictating the formation of the azoxybenzene side-product. Using calculated oxidation potentials, we were able to predict reaction outcomes and improve reaction efficiency simply by modulating the oxidation potential of the arylamine component.
