89-99-6Relevant academic research and scientific papers
Palladium-catalyzed ortho -selective C-H fluorination of oxalyl amide-protected benzylamines
Chen, Changpeng,Wang, Chao,Zhang, Jingyu,Zhao, Yingsheng
, p. 942 - 949 (2015)
A novel and efficient synthetic method for o-fluorobenzylamines via palladium catalyst using an easily accessible oxalyl amide as directing group has been developed. The cheap N-fluorobenzenesulfonimide could be used as an effective [F+] source and t-amyl-OH as the solvent with Pd(OAc)2 as catalyst. Selective mono- or difluorination of oxalyl amide-protected benzylamine derivatives were achieved by modifying the reaction conditions, which presented an efficient method for the preparation of ortho-fluorinated benzylamines.
Generation of Oxidoreductases with Dual Alcohol Dehydrogenase and Amine Dehydrogenase Activity
Tseliou, Vasilis,Schilder, Don,Masman, Marcelo F.,Knaus, Tanja,Mutti, Francesco G.
supporting information, p. 3315 - 3325 (2020/12/11)
The l-lysine-?-dehydrogenase (LysEDH) from Geobacillus stearothermophilus naturally catalyzes the oxidative deamination of the ?-amino group of l-lysine. We previously engineered this enzyme to create amine dehydrogenase (AmDH) variants that possess a new hydrophobic cavity in their active site such that aromatic ketones can bind and be converted into α-chiral amines with excellent enantioselectivity. We also recently observed that LysEDH was capable of reducing aromatic aldehydes into primary alcohols. Herein, we harnessed the promiscuous alcohol dehydrogenase (ADH) activity of LysEDH to create new variants that exhibited enhanced catalytic activity for the reduction of substituted benzaldehydes and arylaliphatic aldehydes to primary alcohols. Notably, these novel engineered dehydrogenases also catalyzed the reductive amination of a variety of aldehydes and ketones with excellent enantioselectivity, thus exhibiting a dual AmDH/ADH activity. We envisioned that the catalytic bi-functionality of these enzymes could be applied for the direct conversion of alcohols into amines. As a proof-of-principle, we performed an unprecedented one-pot “hydrogen-borrowing” cascade to convert benzyl alcohol to benzylamine using a single enzyme. Conducting the same biocatalytic cascade in the presence of cofactor recycling enzymes (i.e., NADH-oxidase and formate dehydrogenase) increased the reaction yields. In summary, this work provides the first examples of enzymes showing “alcohol aminase” activity.
Ultra-small cobalt nanoparticles from molecularly-defined Co-salen complexes for catalytic synthesis of amines
Beller, Matthias,Chandrashekhar, Vishwas G.,Gawande, Manoj B.,Jagadeesh, Rajenahally V.,Kalevaru, Narayana V.,Kamer, Paul C. J.,Senthamarai, Thirusangumurugan,Zbo?il, Radek
, p. 2973 - 2981 (2020/03/27)
We report the synthesis of in situ generated cobalt nanoparticles from molecularly defined complexes as efficient and selective catalysts for reductive amination reactions. In the presence of ammonia and hydrogen, cobalt-salen complexes such as cobalt(ii)-N,N′-bis(salicylidene)-1,2-phenylenediamine produce ultra-small (2-4 nm) cobalt-nanoparticles embedded in a carbon-nitrogen framework. The resulting materials constitute stable, reusable and magnetically separable catalysts, which enable the synthesis of linear and branched benzylic, heterocyclic and aliphatic primary amines from carbonyl compounds and ammonia. The isolated nanoparticles also represent excellent catalysts for the synthesis of primary, secondary as well as tertiary amines including biologically relevant N-methyl amines.
Method for preparing primary amine by catalyzing reductive amination of aldehyde ketone compounds
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Paragraph 0027-0030; 0051-0055, (2020/05/30)
The invention discloses a method for preparing primary amine by catalyzing reductive amination of aldehyde ketone compounds. The method comprises the following steps: 1) mixing nickel nitrate hexahydrate, citric acid and an organic solvent, carrying out heating and stirring until a colloidal material is obtained, drying the colloidal material, roasting the colloidal material in a protective atmosphere, pickling, washing and drying a roasted product, and performing a partial oxidation reaction on a dried product in an oxygen-nitrogen mixed atmosphere to obtain a catalyst for a reductive amination reaction; and 2) mixing aldehyde or ketone compounds, a methanol solution of ammonia and the reductive amination reaction catalyst, introducing hydrogen, and carrying out a reductive amination reaction. The method has the advantages of high primary amine yield, high selectivity, wide aldehyde ketone substrate range, short reaction time, mild reaction conditions, low cost, greenness, economicalperformance and the like; the used reductive amination reaction catalyst can be recycled more than 10 times, and the catalytic activity of the catalyst is not obviously changed in gram-level reactions; and the method is suitable for large-scale application.
PROCESS FOR PREPARATION OF HALOGENATED BENZYLAMINE AND INTERMEDIATES THEROF
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Page/Page column 17, (2020/08/13)
The present invention provides an improved process for the preparation of halogenated benzylamine having the formula I from halogenated benzonitriles, Formula I wherein, X1 is selected from group consisting of hydrogen, chloro or fluoro, provided atleast one X1 is chloro or fluoro.
A benzylamine synthetic method of the compound (by machine translation)
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Paragraph 0036; 0037; 0038, (2018/09/11)
The invention discloses a compound of formula (V) indicated by the benzylamine compound synthetic methods: shown in formula (IV) of the phenmethyl nitrine as raw materials, in the boron tribromide, solvent A and gas B under the protection of the reduction reaction, after the reaction, the solvent C quenching, after treatment [...] (V) indicated by the benzylamine compound. Compared with the existing method, the invention adopts the mild reaction conditions of boron tribromide reagent, avoid the use of a metal catalyst, the operation is simple, the reaction yield is high. (by machine translation)
Highly Stable COF-Supported Co/Co(OH)2 Nanoparticles Heterogeneous Catalyst for Reduction of Nitrile/Nitro Compounds under Mild Conditions
Mullangi, Dinesh,Chakraborty, Debanjan,Pradeep, Anu,Koshti, Vijay,Vinod, Chathakudath P.,Panja, Soumendranath,Nair, Sunil,Vaidhyanathan, Ramanathan
, (2018/09/18)
Ordered nanoporosity in covalent organic framework (COF) offers excellent opportunity for property development. Loading nanoparticles (nPs) onto them is one approach to introducing tailor-made properties into a COF. Here, a COF–Co/Co(OH)2 composite containing about 16 wt% of 2 nPs is prepared on a N-rich COF support that catalyzes the release of theoretical equivalence of H2 from readily available, safe, and cheap NaBH4. Furthermore, the released H2 is utilized for the hydrogenation of nitrile and nitro compounds to amines under ambient conditions in a facile one-pot reaction. The COF “by choice” is built from “methoxy” functionalized dialdehydes which is crucial in enabling the complete retention of the COF structure under the conditions of the catalysis, where the regular Schiff bonds would have hydrolyzed. The N-rich binding pockets in the COF ensure strong nP–COF interactions, which provides stability and enables catalyst recycling. Modeling studies reveal the crucial role played by the COF in exposing the active facets and thereby in controlling the activation of the reducing agent. Additionally, via density functional theory, we provide a rational explanation for how these COFs can stabilize nanoparticles which grow beyond the limiting pore size of the COF and yet result in a truly stable heterogeneous catalyst – a ubiquitous observation. The study underscores the versatility of COF as a heterogeneous support for developing cheap and highly active nonnoble metal catalysts.
Low-Pressure Hydrogenation of Nitriles to Primary Amines Catalyzed by Ruthenium Pincer Complexes. Scope and mechanism
Mukherjee, Arup,Srimani, Dipankar,Ben-David, Yehoshoa,Milstein, David
, p. 559 - 563 (2017/02/26)
The catalytic hydrogenation of nitriles to primary amines constitutes an environmentally benign and atom-economical methodology in synthetic organic chemistry. However, selective hydrogenation can be challenging, and usually elevated pressure and the use of various additives is required. Herein the hydrogenation of aromatic and aliphatic nitriles to form primary amines catalyzed by ruthenium pincer complexes is described. The reactions are conducted at low H2 pressure, low catalytic loadings and, in case of a variety of benzonitriles, under neutral conditions and without any additives. Mechanistic insight is provided.
Small Molecule Inhibitors Simultaneously Targeting Cancer Metabolism and Epigenetics: Discovery of Novel Nicotinamide Phosphoribosyltransferase (NAMPT) and Histone Deacetylase (HDAC) Dual Inhibitors
Dong, Guoqiang,Chen, Wei,Wang, Xia,Yang, Xinglin,Xu, Tianying,Wang, Pei,Zhang, Wannian,Rao, Yu,Miao, Chaoyu,Sheng, Chunquan
, p. 7965 - 7983 (2017/10/18)
Cancer metabolism and epigenetics are among the most intensely pursued research areas in anticancer drug discovery. Here we report the first small molecules that simultaneously inhibit nicotinamide phosphoribosyltransferase (NAMPT) and histone deacetylase (HDAC), two important targets of cancer metabolism and epigenetics, respectively. Through iterative structure-based drug design, chemical synthesis, and biological assays, a highly potent dual NAMPT and HDAC inhibitor was successfully identified. Compound 35 possessed excellent and balanced activities against both NAMPT (IC50 = 31 nM) and HDAC1 (IC50 = 55 nM). It could effectively induce cell apoptosis and autophagy and ultimately led to cell death. Importantly, compound 35 showed excellent in vivo antitumor efficacy in the HCT116 xenograft model. This proof-of-concept study demonstrates the feasibility of discovering an inhibitor targeting cancer metabolism and epigenetics and provides an efficient strategy for multitarget antitumor drug discovery.
Stereoelectronic effects in the reaction of aromatic substrates catalysed by: Halomonas elongata transaminase and its mutants
Contente, Martina Letizia,Planchestainer, Matteo,Molinari, Francesco,Paradisi, Francesca
, p. 9306 - 9311 (2016/10/13)
A transaminase from Halomonas elongata and four mutants generated by an in silico-based design were recombinantly produced in E. coli, purified and applied to the amination of mono-substituted aromatic carbonyl-derivatives. While benzaldehyde derivatives were excellent substrates, only NO2-acetophenones were transformed into the (S)-amine with a high enantioselectivity. The different behaviour of wild-type and mutated transaminases was assessed by in silico substrate binding mode studies.
