- Copper-promoted difunctionalization of unactivated alkenes with silanes
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An efficient copper-catalyzed cascade difunctionalization of N-allyl anilines toward the synthesis of silylated indolines using commercially available silanes has been reported. This strategy provides a new avenue for the synthesis of a diverse array of i
- Chen, Xiaoyu,Guo, Zhuangzhuang,Li, Jingya,Wu, Yangjie,Wu, Yusheng,Xue, Yingying,Zou, Dapeng
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supporting information
p. 989 - 994
(2022/02/11)
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- Cu(OTf)2-Mediated Cross-Coupling of Nitriles and N-Heterocycles with Arylboronic Acids to Generate Nitrilium and Pyridinium Products**
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Metal-catalyzed C–N cross-coupling generally forms C?N bonds by reductive elimination from metal complexes bearing covalent C- and N-ligands. We have identified a Cu-mediated C–N cross-coupling that uses a dative N-ligand in the bond-forming event, which, in contrast to conventional methods, generates reactive cationic products. Mechanistic studies suggest the process operates via transmetalation of an aryl organoboron to a CuII complex bearing neutral N-ligands, such as nitriles or N-heterocycles. Subsequent generation of a putative CuIII complex enables the oxidative C–N coupling to take place, delivering nitrilium intermediates and pyridinium products. The reaction is general for a range of N(sp) and N(sp2) precursors and can be applied to drug synthesis and late-stage N-arylation, and the limitations in the methodology are mechanistically evidenced.
- Bell, Nicola L.,Xu, Chao,Fyfe, James W. B.,Vantourout, Julien C.,Brals, Jeremy,Chabbra, Sonia,Bode, Bela E.,Cordes, David B.,Slawin, Alexandra M. Z.,McGuire, Thomas M.,Watson, Allan J. B.
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supporting information
p. 7935 - 7940
(2021/03/03)
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- An organocatalytic C-C bond cleavage approach: A metal-free and peroxide-free facile method for the synthesis of amide derivatives
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A facile organocatalytic approach has been devised towards the synthesis of amide derivatives using 1,3-dicarbonyls as easily available acyl-sources under peroxide-free reaction conditions. This transformation was accomplished by the cleavage of the C-C bond in the presence of TEMPO as an organocatalyst and excludes the use of transition-metals and harsh reaction conditions. A broad range of substrates with diverse functional groups were well tolerated and delivered the products in high yields.
- Vodnala, Nagaraju,Gujjarappa, Raghuram,Polina, Saibabu,Satheesh, Vanaparthi,Kaldhi, Dhananjaya,Kabi, Arup K.,Malakar, Chandi C.
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supporting information
p. 20940 - 20944
(2020/12/31)
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- Iodine and Br?nsted acid catalyzed C–C bond cleavage of 1,3-diketones for the acylation of amines
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A metal-free N-acylation method of anilines with 1,3-diketones has been developed, by using iodine and p-toluene sulfonic acid as the co-catalysts. The reaction can proceed in 1,4-dioxane at elevated temperature to produce the corresponding amides with 48–89% yields. Further, the gram-scale experiment was carried out under the standard conditions and the possible mechanism was proposed.
- Zhou, Xiao-Yu,Chen, Xia,Yang, Dan
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supporting information
p. 177 - 184
(2019/11/26)
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- Copper-Catalyzed Site-Selective Oxidative C?C Bond Cleavage of Simple Ketones for the Synthesis of Anilides and Paracetamol
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A copper-catalyzed approach for the N-acylation of anilines with acetone and acetophenones via C?C bond cleavage is described. Under the developed conditions both CHCl3 and CH2Cl2 were identified as potential C1-source to promote the transformation. The reaction features a site selective C?C bond cleavage to install the amide moieties with high functional-group compatibility and wide substrate scope. The developed method avoids the use of sensitive and narcotic agents. The method also represents an excellent complement to the previous protocols with lower E-factor (13.91 mg/1 mg) than current industrially used method (E-factor 17.54 mg/1 mg). The developed approach has also been extended for the effective preparation of pyridine derivatives and paracetamol in gram scale. The course of the reaction was monitored by 1H NMR as a preliminary investigation of the reaction mechanism. (Figure presented.).
- Vodnala, Nagaraju,Gujjarappa, Raghuram,Hazra, Chinmoy K.,Kaldhi, Dhananjaya,Kabi, Arup. K.,Beifuss, Uwe,Malakar, Chandi C.
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supporting information
p. 135 - 145
(2018/12/05)
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- Monoprotected l-Amino Acid (l-MPAA), Accelerated Bromination, Chlorination, and Iodination of C(sp2)?H Bonds by Iridium(III) Catalysis
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Halogenated arenes are important structural motifs commonly found in biologically active molecules and used for a variety of transformations in organic synthesis. Herein, we report the mono-protected l-amino acid (l-MPAA) accelerated iridium(III)-catalyzed halogenation of (hetero)anilides at room temperature. This reaction constitutes the first example of an iridium(III)/l-MPAA-catalyzed general halogenation of (hetero)arenes through C(sp2)?H activation. Furthermore, we demonstrate the potential utility of our method through its use in the synthesis of a quinolone derivative.
- Kathiravan, Subban,Nicholls, Ian A.
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supporting information
p. 7031 - 7036
(2017/05/29)
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- Copper-Mediated C-N Coupling of Arylsilanes with Nitrogen Nucleophiles
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A method for the oxidative coupling of arylsilanes with nitrogen nucleophiles is reported. This method occurs with a broad range of heptamethyltrisiloxylarenes and nitrogen nucleophiles, proceeds with the arylsilane as limiting reagent, and does not require a fluoride activator with electron-poor arylsilanes. The combination of this method with C-H silylation generates arylamines from unactivated arenes with site selectivity controlled by steric effects. This combination of steps gives direct access to many compounds that cannot be accessed via alternative C-H functionalization methods, including direct C-H amination or the combination of C-H borylation and amination.
- Morstein, Johannes,Kalkman, Eric D.,Cheng, Chen,Hartwig, John F.
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supporting information
p. 5244 - 5247
(2016/11/02)
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- Additive-free chemoselective acylation of amines and thiols
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Amines with different stereoelectronic nature were efficiently acylated at room temperature using acetic anhydride in the presence of no solvent or additive. Various thiols also react equally well under the same conditions. Chemoselective protection of amines in the presence of thiols, alcohols, and phenols and of thiols in the presence of alcohols, and phenols were achieved using competitive experiments.
- Mojtahedi, Mohammad M.,Saeed Abaee,Heravi, Majid M.,Behbahani, Farahnaz K.
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- Acetylation reactions of amines with ethyl acetate catalysed by ytterbium trifluoromethethanesulfonate
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Catalytic amounts of ytterbium trifluoromethethanesulfonate [Yb(OTf) 3] have been used to catalyse the acetylation reactions of amines with ethyl acetate under mild and neutral conditions.
- Su, Weike,Cai, Hongfei
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p. 414 - 415
(2007/10/03)
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- Oxidation of dichloroanilines and related anilides catalyzed by iron(III) tetrasulfonatophthalocyanine
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We investigated the degradation of polychlorinated pollutants, such as dichloroanilines and related anilides, catalyzed by iron(III) tetrasulfonatophthalocyanine (FePcS) with potassium monopersulfate or hydrogen peroxide as oxidant. The reaction is influenced by the positions of the two chloro-substituents and by the nature of the oxidant. The FePcS- catalyzed oxidation of 3,5-dichloroaniline with potassium monopersulfate leads to the formation of more biodegradable products (carboxylic acids) and to potentially toxic dimers (azo and azoxy compounds). The oxidation of 3,4- dichloroaniline by FePcS/H2O2 converts this pollutant into coupling products. The formation of dimers in the catalytic oxidation of dichloroanilines can be avoided by acylation of the amine function.
- Hadasch, Anke,Meunier, Bernard
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p. 2319 - 2325
(2007/10/03)
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- N,N-diacylpiperazine tachykinin antagonists
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Diacylpiperazines of general structure STR1 are tachykinin receptor antagonists useful in the treatment of inflammatory diseases, pain or migraine, and asthma, and calcium channel blockers useful in the treatment of cardiovascular conditions such as angina, hypertension or ischemia.
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- Kynurenic Acid Derivatives. Structure-Activity Relationships for Excitatory Amino Acid Antagonism and Identification of Potent and Selective Antagonists at the Glycine Site of the N-Methyl-D-aspartate Receptor
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Derivatives of the nonselective excitatory amino acid antagonist kynurenic acid (4-oxo-1,4-dihydroquinoline-2-carboxylic acid, 1) have been synthesized and evaluated for in vitro antagonist activity at the excitatory amino acid receptors sensitive to N-me
- Leeson, Paul D.,Baker, Raymond,Carling, Robert W.,Curtis, Neil R.,Moore, Kevin W.,et al.
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p. 1243 - 1252
(2007/10/02)
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