10338-58-6Relevant articles and documents
Silver-catalyzed intermolecular amination of fluoroarenes
Wang, Yu,Wei, Chenlong,Tang, Ruyun,Zhan, Haosheng,Lin, Jing,Liu, Zhenhua,Tao, Weihua,Fang, Zhongxue
, p. 6191 - 6194 (2018)
A novel highly selective Ag-catalyzed intermolecular amination of fluoroarenes has been developed. This transformation starts from readily available 4-carbonyl fluorobenzene and NaN3 or other nitrogen-source, via amination followed by C-F bond cleavage, thus affording the desired 4-carbonyl arylamine products under mild conditions. The reaction is accelerated using a small amount of water. This pathway is distinct from a previously reported radical amination reaction.
Reductive one batch synthesis of N-arylpiperidines from primary amines and glutaraldehyde
Verardo,Giumanini,Favret,Strazzolini
, p. 447 - 450 (1991)
The construction of the piperidine ring about an aromatic nitrogen atom, by a 5C + N reductiye condensation reaction, using glutaraldehyde (pentanedial) and sodium borohydride in acidic water/methanol medium is described. The reaction is fast, affords good to excellent yields and appears insensitive to electronic effects and severe steric hindrance; it is found to be compatible with a large variety of aryl substituents, including nitro and oxo groups.
Metal-free Synthesis of Aryl Amines: Beyond Nucleophilic Aromatic Substitution
Sandtorv, Alexander H.,Stuart, David R.
, p. 15812 - 15815 (2016)
A mild and metal-free approach to C?N coupling is described that employs diaryliodonium salt electrophiles and secondary aliphatic amine nucleophiles. This reaction results in direct ipso-substitution of the iodonium moiety and unsymmetrical aryl(TMP)iodonium salts are primarily employed. Moreover, arene substituents and substitution patterns that currently pose a challenge to classical metal-free methods are accommodated and the alicyclic amine nucleophiles used here are unprecedented in other contemporary metal-free C?N coupling reactions.
Metal-free late-stage C(sp2)-H functionalization of: N -aryl amines with various sodium salts
Mudithanapelli, Chandrashekar,Kim, Mi-Hyun
, p. 450 - 464 (2020/02/03)
Metal-free consecutive C(sp2)-X (X = Cl, Br, S, N) bond formations of N-aryl amines (cyclic, fused, carbamate, and aminium radicals) were achieved under mild conditions using [bis(trifluoroacetoxy)iodo]benzene (PIFA) and simple nonharmful sodium salts. This direct and selective C(sp2)-H functionalization showed excellent functional group compatibility, cost effectiveness, and late-stage applicability for the synthesis of biologically active natural products. Two mechanisms were proposed to explain the ortho- or para-preference, as well as the accelerating effect of CH3NO2
General Paradigm in Photoredox Nickel-Catalyzed Cross-Coupling Allows for Light-Free Access to Reactivity
Nocera, Daniel G.,Qin, Yangzhong,Sun, Rui
supporting information, p. 9527 - 9533 (2020/04/08)
Self-sustained NiI/III cycles are established as a potentially general paradigm in photoredox Ni-catalyzed carbon–heteroatom cross-coupling reactions through a strategy that allows us to recapitulate photoredox-like reactivity in the absence of light across a wide range of substrates in the amination, etherification, and esterification of aryl bromides, the latter of which has remained, hitherto, elusive under thermal Ni catalysis. Moreover, the accessibility of esterification in the absence of light is especially notable because previous mechanistic studies on this transformation under photoredox conditions have unanimously invoked energy-transfer-mediated pathways.
PIFA-Promoted, Solvent-Controlled Selective Functionalization of C(sp2)-H or C(sp3)-H: Nitration via C-N Bond Cleavage of CH3NO2, Cyanation, or Oxygenation in Water
Mudithanapelli, Chandrashekar,Dhorma, Lama Prema,Kim, Mi-Hyun
supporting information, (2019/05/07)
A novel nitration (via C(sp3)-N breaking/C(sp2)-N formation with CH3NO2) mediated by [bis(trifluoroacetoxy)iodo]benzene (PIFA) is described. The NO2 transfer from CH3NO2 to the aromatic group of the substrate is possible with careful selection of the solvent, NaX, and oxidant. In addition, the solvent-controlled C(sp2)-H functionalization can shift to an α-C(sp3)-H functionalization (cyanation or oxygenation) of the α-C(sp3)-H of cyclic amines.
Spectroscopic Studies of the Chan-Lam Amination: A Mechanism-Inspired Solution to Boronic Ester Reactivity
Vantourout, Julien C.,Miras, Haralampos N.,Isidro-Llobet, Albert,Sproules, Stephen,Watson, Allan J. B.
supporting information, p. 4769 - 4779 (2017/04/11)
We report an investigation of the Chan-Lam amination reaction. A combination of spectroscopy, computational modeling, and crystallography has identified the structures of key intermediates and allowed a complete mechanistic description to be presented, including off-cycle inhibitory processes, the source of amine and organoboron reactivity issues, and the origin of competing oxidation/protodeboronation side reactions. Identification of key mechanistic events has allowed the development of a simple solution to these issues: manipulating Cu(I) → Cu(II) oxidation and exploiting three synergistic roles of boric acid has allowed the development of a general catalytic Chan-Lam amination, overcoming long-standing and unsolved amine and organoboron limitations of this valuable transformation.
Rational Design, Synthesis, and Biological Evaluation of Heterocyclic Quinolones Targeting the Respiratory Chain of Mycobacterium tuberculosis
Hong, W. David,Gibbons, Peter D.,Leung, Suet C.,Amewu, Richard,Stocks, Paul A.,Stachulski, Andrew,Horta, Pedro,Cristiano, Maria L. S.,Shone, Alison E.,Moss, Darren,Ardrey, Alison,Sharma, Raman,Warman, Ashley J.,Bedingfield, Paul T. P.,Fisher, Nicholas E.,Aljayyoussi, Ghaith,Mead, Sally,Caws, Maxine,Berry, Neil G.,Ward, Stephen A.,Biagini, Giancarlo A.,O’Neill, Paul M.,Nixon, Gemma L.
supporting information, p. 3703 - 3726 (2017/05/19)
A high-throughput screen (HTS) was undertaken against the respiratory chain dehydrogenase component, NADH:menaquinone oxidoreductase (Ndh) of Mycobacterium tuberculosis (Mtb). The 11000 compounds were selected for the HTS based on the known phenothiazine Ndh inhibitors, trifluoperazine and thioridazine. Combined HTS (11000 compounds) and in-house screening of a limited number of quinolones (50 compounds) identified ～100 hits and four distinct chemotypes, the most promising of which contained the quinolone core. Subsequent Mtb screening of the complete in-house quinolone library (350 compounds) identified a further ～90 hits across three quinolone subtemplates. Quinolones containing the amine-based side chain were selected as the pharmacophore for further modification, resulting in metabolically stable quinolones effective against multi drug resistant (MDR) Mtb. The lead compound, 42a (MTC420), displays acceptable antituberculosis activity (Mtb IC50 = 525 nM, Mtb Wayne IC50 = 76 nM, and MDR Mtb patient isolates IC50 = 140 nM) and favorable pharmacokinetic and toxicological profiles.
Chan-Evans-Lam Amination of Boronic Acid Pinacol (BPin) Esters: Overcoming the Aryl Amine Problem
Vantourout, Julien C.,Law, Robert P.,Isidro-Llobet, Albert,Atkinson, Stephen J.,Watson, Allan J. B.
, p. 3942 - 3950 (2016/05/24)
The Chan-Evans-Lam reaction is a valuable C-N bond forming process. However, aryl boronic acid pinacol (BPin) ester reagents can be difficult coupling partners that often deliver low yields, in particular in reactions with aryl amines. Herein, we report effective reaction conditions for the Chan-Evans-Lam amination of aryl BPin with alkyl and aryl amines. A mixed MeCN/EtOH solvent system was found to enable effective C-N bond formation using aryl amines while EtOH is not required for the coupling of alkyl amines.
OXADIAZOLE DIARYL COMPOUNDS
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Page/Page column 55-56, (2009/05/29)
The invention relates to compounds of formula (I): wherein R1, R2, Ra , Rb,Rc and W, have the meanings given in claim 1. The compounds are useful e.g. in the treatment of autoimmune disorders, such as multiple sclerosis.
