3241-00-7Relevant academic research and scientific papers
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.
Acidic solvent-free removal of amine-protecting diphenylmethyl groups in the presence of camphorsulfonic acid
Yamagiwa, Noriyuki,Okabe, Takayuki,Suto, Yutaka,Iwasaki, Genji
, p. 1456 - 1458 (2017/11/04)
We developed novel reaction conditions for the removal of the diphenylmethyl group, which is one of the most important protecting groups for amines. The reaction was promoted by adding one equivalent of camphorsulfonic acid in aqueous media, and no acidic
Synthesis, spectral, structural and computational studies on NiS4 and NiS2NP chromophores: Anagostic and C-H?π (chelate) interactions in [Ni(dtc)(PPh3)(NCS)] (dtc = N-(2-phenylethyl)-N-(4-methoxybenzyl)- dithiocarbamate an
Sathiyaraj,Selvaganapathi,Thirumaran,Ciattini, Samuele
, p. 385 - 395 (2016/05/19)
Bis(N-(2-phenylethyl)-N-substituted benzyldithiocarbamato-S,S′)nickel(II) (1-6) and (N-(2-phenylethyl)-N-substituted benzyldithiocarbamato-S,S′)(thiocyanato-N) (triphenylphosphine)nickel(II) (7-12) [substituted benzyl = 2HO-C6H4-CHs
Tandem synthesis of amides and secondary amines from esters with primary amines under solvent-free conditions
Lee, Jeongbin,Muthaiah, Senthilkumar,Hong, Soon Hyeok
, p. 2653 - 2660 (2014/09/17)
An iridium(III)-catalyzed tandem synthesis of amides and amines from esters under solvent-free conditions is described. A commercially available iridium(III) complex, [Cp*IrCl2]2, with sodium acetate showed the best activity for the synthesis of amides and secondary amines. The amide was formed by ester-amide exchange which generates an alcohol in situ which is subsequently transformed to a secondary amine via hydrogen autotransfer. This synthetic protocol with high atom economy generates water as the sole by-product and can afford amides and amines from various esters in a one-pot reaction, expanding the synthetic versatility of ester transformations.
Hydrogen-transfer reductive amination of aldehydes catalysed by nickel nanoparticles
Alonso, Francisco,Riente, Paola,Yus, Miguel
experimental part, p. 1289 - 1292 (2009/04/06)
Nickel nanoparticles have been found to catalyse the reductive amination of aldehydes by transfer hydrogenation with isopropanol at 76°C. Georg Thieme Verlag Stuttgart.
Base-catalyzed anti-Markovnikov hydroamination of vinylarenes - Scope, limitations and computational studies
Horrillo-Martinez, Patricia,Hultzsch, Kai C.,Gil, Adria,Branchadell, Vicenc
, p. 3311 - 3325 (2008/02/10)
The hydroamination of vinylarenes with primary and secondary amines was studied with catalytic amounts as low as 2 mol-% of LiN(SiMe3) 2/TMEDA. Reactions proceeded readily at 120°C in the absence of solvent to give selective anti-Markovnikov addition. Slow addition was observed at 25°C with either electron-deficient p-chlorostyrene or secondary cyclic amines such as pyrrolidine, piperidine, or morpholine. Primary amines were prone to a second hydroamination reaction to form tertiary amine byproducts. The selectivity for the mono(hydroamination) products could be improved with a two-fold excess of the amine. KN(SiMe3)2 showed higher catalytic activity but lower selectivity in comparison to that of LiN(SiMe 3)2, resulting in undesired C-H-activation by-products. The mechanism of the lithium-catalyzed hydroamination and the influence of TMEDA was studied with density functional theory. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.
Microwave-accelerated methodology for the direct reductive amination of aldehydes
Kangasmetsae, Jussi J.,Johnson, Tony
, p. 5653 - 5655 (2007/10/03)
(Chemical Equation Presented) An improved procedure for the direct reductive amination of aldehydes was developed which uses dibutyltin dichloride as catalyst in the presence of phenylsilane as reductant. Rapid reaction is promoted by the use of microwave conditions with anilines, secondary and primary amines being suitable reactants.
2,4-Dinitrobenzenesulfonamides: A simple and practical method for the preparation of a variety of secondary amines and diamines
Fukuyama, Tohru,Cheung, Mui,Jow, Chung-Kuang,Hidai, Yuko,Kan, Toshiyuki
, p. 5831 - 5834 (2007/10/03)
2,4-Dinitrobenzenesulfonamides, readily prepared from primary amines and 2,4-dinitrobenzenesulfonyl chloride, can be alkylated by the Mitsunobu reaction or by the conventional methods to give N,N-disubstituted sulfonamides in excellent yields. Since 2,4-dinitrobenzenesulfonamides can be removed without deprotecting 2-nitrobenzenesulfonamides, a wide variety of diamines could be prepared by the combined use of these protecting/activating groups.
