225236-03-3Relevant articles and documents
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.
Reduction of selenoamides to amines using SmI2-H2O
Thurow, Samuel,Lenardo, Eder J.,Just-Baringo, Xavier,Procter, David J.
, p. 50 - 53 (2017/11/28)
Selenoamides are selectively reduced to amines by SmI2 with H2O. The process is general for primary, secondary, and tertiary aryl and alkyl selenoamide substrates and selectively delivers amine products. The reduction proceeds under mild conditions using SmI2 activated by straightforward addition of H2O, and does not require an additional Lewis base additive.
Palladium meditated CPhenyl-H bond activation of 2-furylimines versus tert-2-furylbenzylamines
Hu, Zhao-Xia,Ma, Nan,Zhang, Jin-Hua,Hu, Wen-Ping,Wang, Hong-Xing
, p. 30 - 35 (2015/01/09)
The reactions of 2-furylimines 2a-f and Na2PdCl4 in the presence of NaOAc at 8-10°C result in nitrogen-palladium coordinated complexes 3a-f. Reduction of 2d-f with NaBH4 followed by N-methylation leads to the corresponding tert-2-furylbenzylamines 5a-c. Treatment of 5a-c with Na2PdCl4 at the same reaction condition as mentioned above affords palladacycles 6a-c where the Pd atoms connect to the phenyl ring rather than the furyl ring. The fact that 5a-c are more active than 2d-f in CPhenyl-H bond activation implies that the electron density of C10 or C8 atom in former is higher than those in latter. Compounds 3a-f, 5a-c, 6a-c were identified by elemental analysis, IR and NMR. In addition, the structures of 3b, 3f and 6c were also confirmed by their single crystal X-ray diffractions.
