367-29-3Relevant academic research and scientific papers
Single-atom Fe-N4site for the hydrogenation of nitrobenzene: theoretical and experimental studies
Dong, Panpan,He, Rong,Liu, Yan,Lu, Ning,Mao, Junjie,Wu, Konglin,Zhang, Wenzhuang,Zheng, Yamin
, p. 7995 - 8001 (2021)
The hydrogenation of nitrobenzene to aniline is an important process in the industry of fine chemicals, but developing inexpensive catalysts with expected activity and selectivity still remains a challenge. By using density functional theory calculations, we demonstrated that the isolated Fe atom not only can weaken the adsorption of reactants and reaction intermediates as compared to Fe nanoparticles, but also remarkably decrease the reaction barrier for the hydrogenation of nitrobenzene to aniline. Thus, the Fe single-atom (Fe SA) catalyst is considered as an ideal catalyst for this reaction. This theoretical prediction has been subsequently confirmed by experimental results obtained for the Fe SAs loaded on N-doped hollow carbon spheres (Fe SAs/NHCSs) which achieved a conversion of 99% with a selectivity of 99% for the hydrogenation of nitrobenzene. The results significantly outperformed the Fe nanoparticles for this reaction. This work provides theoretical insight for the rational design of new catalytic systems with excellent catalytic properties.
NMR studies of chiral discrimination relevant to the liquid chromatographic enantioseparation by a cellulose phenylcarbamate derivative
Yashima, Eiji,Yamamoto, Chiyo,Okamoto, Yoshio
, p. 4036 - 4048 (1996)
Chromatographic enantioseparation of 1,1'-bi-2-naphthol (2) and its mono- and di-O-methylated derivatives (3a, 3b), 2,2'-dihydroxy-6,6'-dimethylbiphenyl (4), and 10,10'-dihydroxy-9,9'-biphenanthryl (5) has been performed on cellulose tris(5-fluoro-2-methylphenylcarbamate) (1) as a chiral stationary phase for high-performance liquid chromatography (HPLC). The complete base-line separation of 2 and 4 was achieved with the elution order of enantiomers such that the (R)-isomers eluted first followed by the (S)-isomers. The resolution of 5 and the O-methylated 3 was difficult on 1. The cellulose derivative 1 dissolved in chloroform also exhibited a chiral discrimination for 2 and 4 in 1H and 13C NMR spectroscopies as well as in HPLC. The hydroxy and some aromatic protons and carbon resonances of 2 and 4 were clearly separated into a pair of peaks due to enantiomers in the presence of 1. The binding geometry and dynamics between 1 and the enantiomers of 2 were investigated on the basis of spin-lattice relaxation time, 1H NMR titrations, and intermolecular NOEs in the presence of 1. These NMR data are fully consistent with the chromatographic elution order. These results, combined with molecular modeling, reveal the chiral discrimination rationale.
Highly chemoselective reduction of azides to amines by Fe(0) nanoparticles in water at room temperature
Panja, Subir,kundu, Debasish,Ahammed, Sabir,Ranu, Brindaban C.
supporting information, p. 3457 - 3460 (2017/08/10)
A highly chemoselective reduction of aryl, heteroaryl, acyl and sulfonyl azides to the corresponding amines has been achieved by Fe(0) nanoparticles in water at room temperature in the absence of external hydride source. Several readily reducible functionalities including alkene, alkyne, S-S linkage, OTBDMS remain unaffected during reduction.
Indazole Compounds as IRAK4 Inhibitors
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Paragraph 0204, (2016/11/28)
The present invention provides indazole compounds of formula (I), which are therapeutically useful as kinase inhibitors, particularly IRAK4 inhibitors, wherein Z1, Z2, R1, R2, R3, ‘m’ and ‘n’ have the meanings given in the specification, and pharmaceutically acceptable salts or stereoisomers thereof that are useful in the treatment and prevention of diseases or disorders, in particular their use in diseases or disorders mediated by kinase enzyme, particularly IRAK4 enzyme. The present invention also provides pharmaceutical compositions comprising at least one of the compounds of the compound of formula (I) together with a pharmaceutically acceptable carrier, diluent or excipient.
INDAZOLE COMPOUNDS AS IRAK4 INHIBITORS
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Page/Page column 37, (2015/07/23)
The present invention provides indazole compound of formula (I), which are therapeutically useful as kinase inhibitor, particularly IRAK4 inhibitors. wherein Z1, Z2, R1, R2, R3, 'm' and 'n' have the meanings given in the specification, and pharmaceutically acceptable salts or stereoisomers thereof that are useful in the treatment and prevention of diseases or disorder, in particular their use in diseases or disorder mediated by kinase enzyme, particularly IRAK4 enzyme. The present invention also provides pharmaceutical composition comprising at least one of the compounds of compound of formula (I) together with a pharmaceutically acceptable carrier, diluent or excipient therefor.
Palladium-catalyzed amination of aryl chlorides and bromides with ammonium salts
Green, Rebecca A.,Hartwig, John F.
supporting information, p. 4388 - 4391 (2015/01/08)
We report the palladium-catalyzed coupling of aryl halides with ammonia and gaseous amines as their ammonium salts. The coupling of aryl chlorides and ortho-substituted aryl bromides with ammonium sulfate forms anilines with higher selectivity for the primary arylamine over the diarylamine than couplings with ammonia in dioxane. The resting state for the reactions of aryl chlorides is different from the resting state for the reactions of aryl bromides, and this change in resting states is proposed to account for a difference in selectivities for reactions of the two haloarenes.
An examination of the palladium/Mor-DalPhos catalyst system in the context of selective ammonia monoarylation at room temperature
Alsabeh, Pamela G.,Lundgren, Rylan J.,McDonald, Robert,Johansson Seechurn, Carin C. C.,Colacot, Thomas J.,Stradiotto, Mark
supporting information, p. 2131 - 2141 (2013/03/14)
An examination of the [{Pd(cinnamyl)Cl}2]/Mor-DalPhos (Mor-DalPhos=di(1-adamantyl)-2-morpholinophenylphosphine) catalyst system in Buchwald-Hartwig aminations employing ammonia was conducted to better understand the catalyst formation process and to guide the development of precatalysts for otherwise challenging room-temperature ammonia monoarylations. The combination of [{Pd(cinnamyl)Cl}2] and Mor-DalPhos afforded [(κ 2-P,N-Mor-DalPhos)Pd(η1-cinnamyl)Cl] (2), which, in the presence of a base and chlorobenzene, generated [(κ2-P,N- Mor-DalPhos)Pd(Ph)Cl] (1 a). Halide abstraction from 1 a afforded [(κ3-P,N,O-Mor-DalPhos)Pd(Ph)]OTf (5), bringing to light a potential stabilizing interaction that is offered by Mor-DalPhos. An examination of [(κ2-P,N-Mor-DalPhos)Pd(aryl)Cl] (1 b-f) and related precatalysts for the coupling of ammonia and chlorobenzene at room temperature established the suitability of 1 a in such challenging applications. The scope of reactivity for the use of 1 a (5 mol %) encompassed a range of (hetero)aryl (pseudo)halides (X=Cl, Br, I, OTs) with diverse substituents (alkyl, aryl, ether, thioether, ketone, amine, fluoro, trifluoromethyl, and nitrile), including chemoselective arylations. Copyright
NOVEL CATALYSTS
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Page/Page column 65, (2012/06/01)
The present invention provides novel compounds and ligands that are useful in transition metal catalyzed cross-coupling reactions. For example, the compounds and ligands of the present invention are useful in palladium or gold catalyzed cross-coupling reactions.
A P,N-Ligand for palladium-catalyzed ammonia arylation: Coupling of deactivated aryl chlorides, chemoselective arylations, and room temperature reactions
Lundgren, Rylan J.,Peters, Brendan D.,Alsabeh, Pamela G.,Stradiotto, Mark
supporting information; experimental part, p. 4071 - 4074 (2010/07/05)
(Figure Presented) Amazing ammonia: A new air-stable P,N-ligand (Mor-DalPhos) is reported that enables the palladium-catalyzed crosscoupling of ammonia to a variety of aryl chloride and aryl tosylate substrates with high chemoselectivity and, for the first time, at room temperature (see scheme; Ad = adamantyl, Ts=para-toluenesulfonyl).
A highly versatile catalyst system for the cross-coupling of aryl chlorides and Amines
Lundgren, Rylan J.,Sappong-Kumankumah, Antonia,Stradiotto, Mark
experimental part, p. 1983 - 1991 (2010/07/03)
The syntheses of 2-(di-tertbutylphosphino)-N,N-dimethylaniline (L1, 71%) and 2-(di-1-adamantylphosphino)-N,N-dimethylaniline (L2, 74%), and their application in BuchwaldHartwig amination, are reported. In combination with [Pd(allyl)Cl]2 or [Pd(cinnamyl)Cl]2, these structurally simple and air-stable P,N ligands enable the cross-coupling of aryl and heteroaryl chlorides, including those bearing as substituents enolizable ketones, ethers, esters, carboxylic acids, phenols, alcohols, olefins, amides, and halogens, to a diverse range of amine and related substrates that includes primary alkyl- and arylamines, cyclic and acyclic secondary amines, N-H imines, hydrazones, lithium amide, and ammonia. In many cases, the reactions can be performed at low catalyst loadings (0.5-0.02 mol % Pd) with excellent functional group tolerance and chemoselectivity. Examples of cross-coupling reactions involving 1,4-bromochlorobenzene and iodobenzene are also reported. Under similar conditions, inferior catalytic performance was achieved when using Pd(OAc)2, PdCl2, [PdCl2(cod)] (cod = 1,5-cyclooctadiene), [PdCl 2(MeCN)2], or [Pd2(dba)3] (dba = dibenzylideneacetone) in combination with L1 or L2, or by use of [Pd(allyl)Cl]2 or [Pd(cinnamyl)Cl]2 with variants of L1 and L2 bearing less basic or less sterically demanding substituents on phosphorus or lacking an ortto-dimethylamino fragment. Given current limitations associated with established ligand classes with regard to maintaining high activity across the diverse possible range of C-N coupling applications, L1 and L2 represent unusually versatile ligand systems for the cross-coupling of aryl chlorides and amines
