- Electrochemical Cross-Dehydrogenative Aromatization Protocol for the Synthesis of Aromatic Amines
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The introduction of amines onto aromatics without metal catalysts and chemical oxidants is synthetically challenging. Herein, we report the first example of an electrochemical cross-dehydrogenative aromatization (ECDA) reaction of saturated cyclohexanones and amines to construct anilines without additional metal catalysts and chemical oxidants. This reaction exhibits a broad scope of cyclohexanones including heterocyclic ketones, affording a variety of aromatic amines with various functionalities, and shows great potential in the synthesis of biologically active compounds.
- Tao, Shao-Kun,Chen, Shan-Yong,Feng, Mei-Lin,Xu, Jia-Qi,Yuan, Mao-Lin,Fu, Hai-Yan,Li, Rui-Xiang,Chen, Hua,Zheng, Xue-Li,Yu, Xiao-Qi
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supporting information
p. 1011 - 1016
(2022/02/05)
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- Amination of Aryl Halides Mediated by Electrogenerated Nickel from Sacrificial Anode
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Electrochemical C(sp2)?N couplings mediated by nickel salts generated from the sacrificial anode has been described for the first time. In this approach, the sacrificial nickel anode is employed as the sole source of nickel and the process, operationally simple to set up, enables the preparation of functionalized arylamine derivatives with moderate to good yields, under mild reaction conditions and without additional ligand. A cooperative process between the two electrodes is involved in the proposed mechanism.
- Daili, Farah,Sengmany, Stéphane,Léonel, Eric
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p. 2462 - 2469
(2021/06/28)
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- Organic semiconductor photocatalyst can bifunctionalize arenes and heteroarenes
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Photoexcited electron-hole pairs on a semiconductor surface can engage in redox reactions with two different substrates. Similar to conventional electrosynthesis, the primary redox intermediates afford only separate oxidized and reduced products or, more rarely, combine to one addition product. Here, we report that a stable organic semiconductor material, mesoporous graphitic carbon nitride (mpg-CN), can act as a visible-light photoredox catalyst to orchestrate oxidative and reductive interfacial electron transfers to two different substrates in a two- or three-component system for direct twofold carbon–hydrogen functionalization of arenes and heteroarenes. The mpg-CN catalyst tolerates reactive radicals and strong nucleophiles, is straightforwardly recoverable by simple centrifugation of reaction mixtures, and is reusable for at least four catalytic transformations with conserved activity.
- Ghosh, Indrajit,Khamrai, Jagadish,Savateev, Aleksandr,Shlapakov, Nikita,Antonietti, Markus,K?nig, Burkhard
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p. 360 - 366
(2019/08/15)
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- Dihalogen-bridged NHC-palladium(i) dimers: Synthesis, characterisation and applications in cross-coupling reactions
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A di-iodo-bridged PdI dimer bearing an N-heterocyclic carbene ligand was made accessible via the reduction of [(IPr)PdI2]2 in basic methanol solution. The structural features of [(IPr)PdI]2 were explored by single-crystal X-ray analysis. It was found to be a convenient one-component precatalyst with high activity in Suzuki-Miyaura, Buchwald-Hartwig, and Sonogashira reactions.
- Pirkl, Nico,Del Grosso, Alessandro,Mallick, Bert,Doppiu, Angelino,Goo?en, Lukas J.
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supporting information
p. 5275 - 5278
(2019/05/08)
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- Silver-catalyzed intermolecular amination of fluoroarenes
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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.
- Wang, Yu,Wei, Chenlong,Tang, Ruyun,Zhan, Haosheng,Lin, Jing,Liu, Zhenhua,Tao, Weihua,Fang, Zhongxue
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supporting information
p. 6191 - 6194
(2018/09/10)
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- Design, synthesis and biological evaluation of a series of novel 2-benzamide-4-(6-oxy-N-methyl-1-naphthamide)-pyridine derivatives as potent fibroblast growth factor receptor (FGFR) inhibitors
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Starting from the phase II clinical FGFR inhibitor lucitanib (2), we conducted a medicinal chemistry approach by opening the central quinoline skeleton coupled with a scaffold hopping process thus leading to a series of novel 2-benzamide-4-(6-oxy-N-methyl-1-naphthamide)-pyridine derivatives. Compound 25a was identified to show selective and equally high potency against FGFR1/2 and VEGFR2 with IC50 values less than 5.0 nM. Significant antiproliferative effects on both FGFR1/2 and VEGFR2 aberrant cancer cells were observed. In the SNU-16 xenograft model, compound 25a showed tumor growth inhibition rates of 25.0% and 81.0% at doses of 10 mg/kg and 50 mg/kg, respectively, with 5% and 10%body weight loss. In view of the synergistic potential of FGFs and VEGFs in tumor angiogenesis observed in preclinical studies, the FGFR/VEGFR2 dual inhibitor 25a may achieve better clinical benefits.
- Wei, Manman,Peng, Xia,Xing, Li,Dai, Yang,Huang, Ruimin,Geng, Meiyu,Zhang, Ao,Ai, Jing,Song, Zilan
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- Pyrazolo [3,4 - the b] pyridine and [...] composition preparation method and use of (by machine translation)
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The present invention provides a pyrazolo [3,4 - the b] pyridine and [...] compound of preparation and use, in particular, the present invention provides a following formula (I) compounds are shown, wherein the definition of each group as described in the specification. The compounds of the invention has excellent tyrosine kinase inhibiting activity, so can be used for preparing a series of treating diseases associated with the tyrosine kinase activity of the drug. (by machine translation)
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Paragraph 0428; 0429; 0430; 0431
(2017/07/22)
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- Rapid and convenient synthesis of N-arylmorpholines under microwave irradiation
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A series of N-arylmorpholines 1a-1n was obtained by cyclocondensation of arylamines and diethylene glycol dimesylate under microwave irradiation in an aqueous potassium carbonate medium. The reaction is rapid and convenient, and a variety of functional groups are tolerated in the process.
- Li, Hong Bo,Liang, Wu,Ma, Chang Peng,Kai, Yong Mao,Li, Lei,Zhang, Yong Gang
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p. 995 - 998
(2013/08/23)
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- Nickel-catalyzed amination of aryl phosphates through cleaving aryl C-O bonds
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The amination of triaryl phosphates was achieved using a Ni(II)-(σ-Aryl) complex/NHC catalyst system in dioxane at 110 °C in the presence of NaH as base. Electron-neutral, -rich, and -deficient triaryl phosphates were coupled with a wider range of amine partners including cyclic and acyclic secondary amines, aliphatic primary amines, and anilines in good to excellent yields.
- Huang, Jin-Hua,Yang, Lian-Ming
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supporting information; experimental part
p. 3750 - 3753
(2011/09/14)
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- Evaluation of aromatic amination catalyzed by palladium on carbon: A practical synthesis of triarylamines
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A heterogeneous palladium on carbon (Pd/C)-catalyzed coupling between amines and aromatic halides including aromatic chlorides has been achieved using sodium tert-butoxide (NaO-t-Bu) and 1,1′-bis(diphenylphosphino)ferrocene (dppf) as a ligand in cyclopentyl methyl ether (CPME). The use of potassium tert-butoxide (KO-t-Bu) in place of NaO-t-Bu brought about the benzyne-mediated aromatic amination even without Pd/C and dppf, giving a mixture of regioisomers when 4-substituted bromobenzenes were employed as the substrate. The combination of Pd/C, dppf, NaO-t-Bu could be utilized for the syntheses of a broad range of triarylamines by replacing CPME with mesitylene which can provide a higher reaction temperature. The Pd/C could be quantitatively recovered and reused until at least the fourth cycle without any loss in catalytic activity. The quite low leaching of palladium (1.1%) was demonstrated by an inductively coupled plasma-atomic emission spectrometric analysis.
- Monguchi, Yasunari,Kitamoto, Katsunori,Ikawa, Takashi,Maegawa, Tomohiro,Sajiki, Hironao
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supporting information; experimental part
p. 2767 - 2777
(2009/12/08)
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- Triaminophosphine ligands for carbon-nitrogen and carbon-carbon bond formation
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Methods and compounds are provided for the formation of carbon-nitrogen or carbon-carbon bonds comprising reacting an amine or an aryl boronic acid with an aryl halide in the presence of a palladium catalyst, a base, and a compound of formula II:
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Page/Page column 31-34; 35-36
(2008/12/05)
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- SAR and X-ray structures of enantiopure 1,2-cis-(1R,2S)-cyclopentyldiamine and cyclohexyldiamine derivatives as inhibitors of coagulation Factor Xa
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In the search of Factor Xa (FXa) inhibitors structurally different from the pyrazole-based series, we identified a viable series of enantiopure cis-(1R,2S)-cycloalkyldiamine derivatives as potent and selective inhibitors of FXa. Among them, cyclohexyldiam
- Qiao, Jennifer X.,Chang, Chong-Hwan,Cheney, Daniel L.,Morin, Paul E.,Wang, Gren Z.,King, Sarah R.,Wang, Tammy C.,Rendina, Alan R.,Luettgen, Joseph M.,Knabb, Robert M.,Wexler, Ruth R.,Lam, Patrick Y.S.
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p. 4419 - 4427
(2008/02/10)
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- Copper-catalyzed electrophilic amination of organozinc nucleophiles: Documentation of O-benzoyl hydroxylamines as broadly useful R2N(+) and RHN(+) synthons
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This paper details new copper-catalyzed electrophilic amination reactions of diorganozinc reagents using O-benzoyl hydroxylamines as electrophilic nitrogen sources that may be accessed in one step. Simple and functionalized aryl, heteroaryl-, benzyl, n-alkyl, sec-alkyl, and tert-alkyl nucleophiles couple with R2NOC(O)Ph and RHNOC(O)Ph reagents in the presence of catalytic quantities of copper salts to provide tertiary and secondary amines, respectively, in generally good yields. In many cases, the product may be isolated analytically pure after a simple extractive workup. The amination process is shown to tolerate a significant degree of steric demand. The amination of nominally unreactive Caryl-H bonds via a sequential directed ortho metalation/transmetalation/catalytic amination reaction sequence is detailed. The direct Cu-catalyzed amination of Grignard reagents using cocatalysis by ZnCl2 is described.
- Herman, Ashley M.,Johnson, Jeffrey S.
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p. 219 - 224
(2007/10/03)
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- Copper-catalyzed electrophilic amination of functionalized diarylzinc reagents
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(Chemical Equation Presented). The copper-catalyzed electrophilic amination of functionalized diarylzinc reagents with O-acyl hydroxylamines allows for the preparation of functionalized tertiary arylamines in high yields, and is noteworthy for the mild re
- Berman, Ashley M.,Johnson, Jeffrey S.
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p. 364 - 366
(2007/10/03)
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- Nickel-catalyzed electrophilic amination of organozinc halides
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The nickel-catalyzed electrophilic amination of organozinc halides with O-benzoyl N,N-dialkyl hydroxylamines allows for the preparation of a variety of aryl and alkyl tertiary amines in good yield. The reaction is noteworthy for the mild reaction conditions employed (room temperature) and the ease of product purification (acid/base extractive work up). Georg Thieme Verlag Stuttgart.
- Berman, Ashley M.,Johnson, Jeffrey S.
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p. 1799 - 1801
(2007/10/03)
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- LACTAM-CONTAINING CYCLIC DIAMINES AND DERIVATIVES AS FACTOR XA INHIBITORS
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The present application describes lactam-containing cyclic diamines and derivatives thereof of Formula I: or pharmaceutically acceptable salt forms thereof, wherein M is a non-aromatic carbocycle or heterocycle. Compounds of the present invention are useful as inhibitors of trysin-like serine proteases, specifically factor Xa.
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Page/Page column 107
(2010/02/08)
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- Application of a New Bicyclic Triaminophosphine Ligand in Pd-Catalyzed Buchwald-Hartwig Amination Reactions of Aryl Chlorides, Bromides, and Iodides
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The new bicyclic triaminophosphine ligand P(i-BuNCH2) 3CMe (3) has been synthesized in three steps from commercially available materials and its efficacy in palladium-catalyzed reactions of aryl halides with an array of amines has been demonstrated. Electron-poor, electron-neutral, and electron-rich aryl bromides, chlorides, and iodides participated in the process. The reactions encompassed aromatic amines (primary or secondary) and secondary amines (cyclic or acyclic). It has also been shown that the weak base Cs2CO3 can be employed with ligand 3, allowing a variety of functionalized substrates (e.g., those containing esters and nitro groups) to be utilized in our amination protocols. This ligand provides a remarkably general, efficient, and mild palladium catalyst for aryl iodide amination. Although 3 is slightly air and moisture sensitive, easy procedures can be adopted that avoid the need of a glovebox. Comparisons of the efficacy of 3 in these reactions with that of the proazaphosphatrane P(i-BuNCH2CH2)3N (2) reveal that in addition to the opportunity for transannulation in 2 (but not in 3), other significant stereoelectronic contrasts exist between these two ligands which help account for differences in the activities of the Pd/2 and Pd/3 catalytic systems.
- Urgaonkar, Sameer,Xu, Ju-Hua,Verkade, John G.
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p. 8416 - 8423
(2007/10/03)
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- Process for the synthesis of morpholinylbenzenes
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A new improved process for synthesizing morpholinylbenzenes of the formula I by reacting morpholine of II with a substituted benzene of formula III, wherein morpholine is used as a reactant and as the only one solvent.
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- High yields of meta-substituted amination products in the S(N)Ar substitution of benzenes
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Morpholine substitution in fluorobenzenes containing a meta-substituted electron withdrawing group proceeds in DMSO at 100 °C over 60 h to give meta-substitution products (by fluoride ion displacement) in pure isolated yields of 19-98%.
- Brown,Foubister,Ratcliffe
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p. 1219 - 1222
(2007/10/03)
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- Synthesis of meta-substituted aniline derivatives by nucleophilic substitution
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Substitution by amines of fluorobenzenes containing a meta- substituted electron withdrawing group (EWG), in DMSO at 100 °C over 60 h gave meta-substituted aniline derivatives in isolated yields of up to 98%. The scope of the reaction is explored in terms of reaction conditions and substrates. It is postulated that facile meta-substitutions are facilitated through field stabilisation of the intermediate anion by EWG substituents.
- Belfield, Andrew J.,Brown, George R.,Foubister, Alan J.,Ratcliffe, Paul D.
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p. 13285 - 13300
(2007/10/03)
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- High pressure organic chemistry; XII. A convenient synthesis of aromatic amines from activated aromatic fluorides
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Aromatic fluorides containing electron-withdrawing substituents are cleanly reacted with amines at 10 kbar pressure to give various aromatic amines.
- Kotsuki,Kobayashi,Matsumoto,Suenaga,Nishizawa
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p. 1147 - 1148
(2007/10/02)
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