55-81-2Relevant academic research and scientific papers
A new amide from Zanthoxylum armatum
Kalia, Narendra K.,Singh, Bikram,Sood, Ram P.
, p. 311 - 312 (1999)
A new amide designated as armatamide (1) - along with two lignans, asarinin and fargesin, α- and β-amyrins, lupeol, and β-sitosterol-β-D- glucoside - has been isolated from the bark of Zanthoxylum armatum. The structure of the new compound was deduced by spectral and chemical analysis as N-(4'-methoxyphenyl ethyl)-3, 4-methylenedioxy cinnamoyl amide.
Reaction of Diisobutylaluminum Borohydride, a Binary Hydride, with Selected Organic Compounds Containing Representative Functional Groups
Amberchan, Gabriella,Snelling, Rachel A.,Moya, Enrique,Landi, Madison,Lutz, Kyle,Gatihi, Roxanne,Singaram, Bakthan
supporting information, p. 6207 - 6227 (2021/05/06)
The binary hydride, diisobutylaluminum borohydride [(iBu)2AlBH4], synthesized from diisobutylaluminum hydride (DIBAL) and borane dimethyl sulfide (BMS) has shown great potential in reducing a variety of organic functional groups. This unique binary hydride, (iBu)2AlBH4, is readily synthesized, versatile, and simple to use. Aldehydes, ketones, esters, and epoxides are reduced very fast to the corresponding alcohols in essentially quantitative yields. This binary hydride can reduce tertiary amides rapidly to the corresponding amines at 25 °C in an efficient manner. Furthermore, nitriles are converted into the corresponding amines in essentially quantitative yields. These reactions occur under ambient conditions and are completed in an hour or less. The reduction products are isolated through a simple acid-base extraction and without the use of column chromatography. Further investigation showed that (iBu)2AlBH4 has the potential to be a selective hydride donor as shown through a series of competitive reactions. Similarities and differences between (iBu)2AlBH4, DIBAL, and BMS are discussed.
A State-of-the-Art Heterogeneous Catalyst for Efficient and General Nitrile Hydrogenation
Formenti, Dario,Mocci, Rita,Atia, Hanan,Dastgir, Sarim,Anwar, Muhammad,Bachmann, Stephan,Scalone, Michelangelo,Junge, Kathrin,Beller, Matthias
supporting information, p. 15589 - 15595 (2020/10/02)
Cobalt-doped hybrid materials consisting of metal oxides and carbon derived from chitin were prepared, characterized and tested for industrially relevant nitrile hydrogenations. The optimal catalyst supported onto MgO showed, after pyrolysis at 700 °C, magnesium oxide nanocubes decorated with carbon-enveloped Co nanoparticles. This special structure allows for the selective hydrogenation of diverse and demanding nitriles to the corresponding primary amines under mild conditions (e.g. 70 °C, 20 bar H2). The advantage of this novel catalytic material is showcased for industrially important substrates, including adipodinitrile, picolinonitrile, and fatty acid nitriles. Notably, the developed system outperformed all other tested commercial catalysts, for example, Raney Nickel and even noble-metal-based systems in these transformations.
Ruthenium(II)-cored supramolecular organic framework-mediated recyclable visible light photoreduction of azides to amines and cascade formation of lactams
Wu, Yi-Peng,Yan, Meng,Gao, Zhong-Zheng,Hou, Jun-Li,Wang, Hui,Zhang, Dan-Wei,Zhang, Junliang,Li, Zhan-Ting
, p. 1383 - 1386 (2019/05/06)
Ru(bpy)3]2+-cored supramolecular organic framework SMOF-1, assembled from a [Ru(bpy)3]2+-derived hexaarmed molecule and cucurbit[8]uril, has been demonstrated to heterogeneously catalyze visible light-induced reduction of phenyl, benzyl, 2-phenylethyl and 3-phenylpropyl azides in acetonitrile to produce the corresponding amines in good to high yields. For the last two kinds of azides that bear a CO2Me group at the para-position of the benzene ring, cascade reactions take place to generate the corresponding lactams in high yields. Compared with homogeneous control [Ru(bpy)3]Cl2, SMOF-1 exhibits remarkably increased photocatalysis activity as a result of synergistic effect of the [Ru(bpy)3]2+ units that form cubic cages to host the azide molecules and related intermediates. Moreover, SMOF-1 displays high recyclability and considerable photocatalysis activity after 3 to 12 runs.
Method for preparing substituted primary aliphatic amine
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Paragraph 0048-0055, (2019/01/21)
The invention belongs to the fields of medicinal and natural compound chemical intermediates and related chemical technologies, and relates to a preparation method of substituted primary amine. The method adopts benzonitrile and its derivative as raw materials, takes nanoporous palladium as a catalyst, takes hydrogen as a hydrogen source, and performs selective hydrogenation to prepare the substituted primary amine. The molar concentration of benzonitrile and its derivative in a solvent is 0.01-2 mmol/mL, and the molar ratio of benzonitrile and its derivative to the catalyst is 1:0.01-1:0.5; the size pore skeleton of the nanoporous palladium is 1 nm to 50 nm; and the pressure of hydrogen gas is 0.1 to 20.0 MPa. The method has the beneficial effects that the obtained product has high selectivity, the reaction condition is very mild, no additives is needed, the operation and the post-treatment are simple, the catalyst reproducibility is good, the multi-time catalytic effect with repeateduse is not significantly reduced, and the method provides possibility for industrialization.
Facile synthesis of supported Ru-Triphos catalysts for continuous flow application in selective nitrile reduction
Konrath, Robert,Heutz, Frank J.L.,Steinfeldt, Norbert,Rockstroh, Nils,Kamer, Paul C.J.
, p. 8195 - 8201 (2019/09/19)
The selective catalytic hydrogenation of nitriles represents an important but challenging transformation for many homogeneous and heterogeneous catalysts. Herein, we report the efficient and modular solid-phase synthesis of immobilized Triphos-type ligands in very high yields, involving only minimal work-up procedures. The corresponding supported ruthenium-Triphos catalysts are tested in the hydrogenation of various nitriles. Under mild conditions and without the requirement of additives, the tunable supported catalyst library provides selective access to both primary amines and secondary imines. Moreover, the first application of a Triphos-type catalyst in a continuous flow process is presented demonstrating high catalyst life-time over at least 195 hours without significant activity loss.
Combined Photoredox/Enzymatic C?H Benzylic Hydroxylations
Betori, Rick C.,May, Catherine M.,Scheidt, Karl A.
supporting information, p. 16490 - 16494 (2019/11/03)
Chemical transformations that install heteroatoms into C?H bonds are of significant interest because they streamline the construction of value-added small molecules. Direct C?H oxyfunctionalization, or the one step conversion of a C?H bond to a C?O bond, could be a highly enabling transformation due to the prevalence of the resulting enantioenriched alcohols in pharmaceuticals and natural products,. Here we report a single-flask photoredox/enzymatic process for direct C?H hydroxylation that proceeds with broad reactivity, chemoselectivity and enantioselectivity. This unified strategy advances general photoredox and enzymatic catalysis synergy and enables chemoenzymatic processes for powerful and selective oxidative transformations.
Deacetylative Amination of Acetyl Arenes and Alkanes with C-C Bond Cleavage
Hyodo, Kengo,Hasegawa, Genna,Maki, Hiroya,Uchida, Kingo
supporting information, p. 2818 - 2822 (2019/04/25)
The Br?nsted acid-catalyzed synthesis of primary amines from acetyl arenes and alkanes with C-C bond cleavage is described. Although the conversion from an acetyl group to amine has traditionally required multiple steps, the method described herein, which uses an oxime reagent as an amino group source, achieves the transformation directly via domino transoximation/Beckmann rearrangement/Pinner reaction. The method was also applied to the synthesis of γ-aminobutyric acids, such as baclophen and rolipram.
Synthesis of cobalt nanoparticles by pyrolysis of Vitamin B12: A non-noble-metal catalyst for efficient hydrogenation of nitriles
Ferraccioli, Raffaella,Borovika, Diana,Surkus, Annette-Enrica,Kreyenschulte, Carsten,Topf, Christoph,Beller, Matthias
, p. 499 - 507 (2018/02/07)
A facile preparation of vitamin B12-derived carbonaceous cobalt particles supported on ceria is reported. The resulting composite material is obtained upon wet impregnation of ceria with natural cyanocobalamin and consecutive pyrolysis under inert conditions. The novel catalyst shows good to excellent performance in the industrially relevant heterogeneous hydrogenation of nitriles to the corresponding primary amines.
Selective Hydrogenation of Nitriles to Primary Amines by using a Cobalt Phosphine Catalyst
Adam, Rosa,Bheeter, Charles Beromeo,Cabrero-Antonino, Jose R.,Junge, Kathrin,Jackstell, Ralf,Beller, Matthias
, p. 842 - 846 (2017/03/17)
A general procedure for the catalytic hydrogenation of nitriles to primary amines by using a non-noble metal-based system is presented. Co(acac)3 in combination with tris[2-(dicyclohexylphosphino)ethyl]phosphine efficiently catalyzes the selective hydrogenation of a wide range of (hetero)aromatic and aliphatic nitriles to give the corresponding amines.
