1137-77-5Relevant articles and documents
Nickel-catalyzed monoarylation of ammonia
Borzenko, Andrey,Rotta-Loria, Nicolas L.,Macqueen, Preston M.,Lavoie, Christopher M.,McDonald, Robert,Stradiotto, Mark
, p. 3773 - 3777 (2015)
Structurally diverse (hetero)aryl chloride, bromide, and tosylate electrophiles were employed in the Ni-catalyzed monoarylation of ammonia, including chemoselective transformations. The employed JosiPhos/[Ni(cod)2] catalyst system enables the use of commercially available stock solutions of ammonia, or the use of ammonia gas in these reactions, thereby demonstrating the versatility and potential scalability of the reported protocol. Proof-of-principle experiments established that air-stable [(JosiPhos)NiCl2] precatalysts can be employed successfully in such transformations. Lighten Up: The substrate scope of the title reaction includes (hetero)aryl chloride, bromide, and tosylate electrophiles. The versatility and potential scalability of the reported method is demonstrated by the use of either commercially available stock solutions of ammonia or ammonia gas.
Liquid-Assisted Grinding Accelerating: Suzuki-Miyaura Reaction of Aryl Chlorides under High-Speed Ball-Milling Conditions
Jiang, Zhi-Jiang,Li, Zhen-Hua,Yu, Jing-Bo,Su, Wei-Ke
, p. 10049 - 10055 (2016)
The effect of liquid-assisted grinding has been studied using mechanical Suzuki-Miyaura reaction of aryl chlorides as the model reaction. Catalytic systems of Davephos and PCy3 are tested respectively showing strong influences from different liquids. Unexpected improvement of yield over 55% is observed using alcohols as additives, which is explained by in situ formed alkoxides and their participation in oxidative addition. Further expansion of substrates using Pd(OAc)2/PCy3/MeOH system gives desired products in good to high yields.
Base-Free Suzuki–Miyaura Coupling Reaction Using Palladium(II) Supported Catalyst in Water
Tomar, Ravi,Singh, Nidhi,Kumar, Neeraj,Tomar, Vartika,Chandra, Ramesh
, (2019)
Abstract: The carbon–carbon bond formation via Suzuki–Miyaura reaction was performed in water as green solvent. Pd(OAc)2(PPh3)2 supported on magnesium hydroxide and cerium carbonate hydroxide composite was prepared and characterized by various techniques. The cross-coupling reaction of aryl halides carried out in water using mild conditions. The effects of temperature, solvents, the amount of catalyst and leaving groups were studied to find the optimization conditions for cross-coupling reaction. Various aryl halides were smoothly transformed into the biaryls in good yields. In addition, the catalyst also exhibited stability and catalytic performance in the cross-coupling of aryl halides. Graphical Abstract: [Figure not available: see fulltext.] A new approach is developed for carbon–carbon bond formation via Suzuki–Miyaura reaction.2 Pd(OAc)2(PPh3)2?supported on mixed magnesium hydroxide and cerium carbonate hydroxide were prepared and characterized by XRD, XPS, SEM–EDX techniques. The cross-coupling reaction of aryl halides can be carried out in water and under mild conditions (80 °C).
Magnetic chitosan-functionalized cobalt-NHC: Synthesis, characterization and catalytic activity toward Suzuki and Sonogashira cross-coupling reactions of aryl chlorides
Hajipour, Abdol R.,Malek, Shaghayegh Sadeghi
, (2021)
Aryl chlorides are one of the most stable and available electrophiles, however, their coupling with nucleophiles remains a challenge in organic synthesis. Herein, we prepared a Cobalt-NHC (N-Heterocyclic carbene) complex anchored on magnetic chitosan nanoparticles and assayed its catalytic activity for the reactions of substituted phenylboronic acid and also phenlacetylene with derivatives of aryl chlorides. These reactions are of great importance since they are employed for the synthesis of unsymmetrical diarylethynes and biphenyls, which belong to a prime class of building blocks. The synthesized nanocatalyst was found to be highly efficient in Suzuki and Sonogashira coupling in terms of their activity and recyclability in polyethylene glycol (PEG) as a green reaction media under conditions of temperatures (70 and 100 °C) and Co loading (3 and 6 mol%). To the best of our knowledge, this is the first attempt of using cobalt-NHC complex for catalyzing the abovementioned reactions. Moreover, replacing the earth-abundant Cobalt-based catalyst as an alternative to high cost palladium make this approach promising from sustainable chemistry view.
Assembly immobilized palladium(0) on carboxymethylcellulose/Fe3O4 hybrid: An efficient tailor-made magnetically catalyst for the Suzuki–Miyaura couplings
Zhang, Zhuan,Zhang, Yizong,Liu, Xiaoping,Shen, Binbin,Zhang, Tianzhu,Li, Yiqun
, (2018)
The Pd nanoparticles (Pd NPs) embedded on magnetically retrievable carboxymethylcellulose/Fe3O4 (Pd0@CMC/Fe3O4) organic/inorganic hybrid were prepared via the conventional simple process. The presence of the hydroxyl and carboxyl groups within the framework of the magnetic hybrid enables the facile preparation and stabilization of Pd NPs in this organic/inorganic hybrid. This hybrid catalyst was very effective in the Suzuki–Miyaura reaction of a variety of aryl halides with arylboronic acid to afford excellent product yields. The catalyst showed good stability and could be easily recovered with an external magnetic field and reused for several times without a significant loss in its catalytic activity. Furthermore, the Pd0@CMC/Fe3O4 hybrid catalyst was fully characterized by UV–Vis, FT–IR, XRD, SEM, EDX, TEM, XPS and TGA techniques. The hot filtration test suggests that a homogeneous mechanism is operative in Suzuki–Miyaura reaction.
Suzuki cross-coupling reaction over Pd-Schiff-base anchored mesoporous silica catalyst
Das, Soma,Bhunia, Susmita,Maity, Tanmoy,Koner, Subratanath
, p. 188 - 197 (2014)
A new hybrid catalyst has been prepared by tethering a palladium(II) Schiff-base complex via post-synthesis modification of mesoporous silica, MCM-41. The Schiff-base has been derived from o-vanillin and 3-[(2-aminoethylamino)propyl]trimethoxysilane (ATMS) which is chemically anchored on MCM-41 via silicon alkoxide route. The anchored Schiff-base imposed a stable planar coordination sphere on the central palladium ion. The catalyst has been characterized by elemental analysis, small angle X-ray diffraction, FT-IR, UV-vis, N2 sorption study, transmission electron microscopy (TEM) studies and scanning electron microscopy (SEM) studies. X-ray and TEM measurement showed the mesoporosity of the catalyst. The activity of the catalyst has been assessed in the Suzuki CC cross coupling reaction using various phenyboronic acid in heterogeneous condition. High selectivity for the biaryl products containing both electron-donating and electron-withdrawing substituents, high turnover, mild reaction conditions and possibility of easy recycle makes the catalyst highly desirable to address the industrial needs and environmental concerns.
Novel 5-methyl-2-phenylphenanthridium derivatives as FtsZ-targeting antibacterial agents from structural simplification of natural product sanguinarine
Liu, Jingru,Ma, Ruxin,Bi, Fangchao,Zhang, Fa,Hu, Chaoyu,Venter, Henrietta,Semple, Susan J.,Ma, Shutao
, p. 1825 - 1831 (2018)
A novel series of 5-methyl-2-phenylphenanthridium derivatives were displayed outstanding activity against a panel of antibiotic-sensitive and -resistant bacteria strains compared with their precursor sanguinarine, ciprofloxacin and oxacillin sodium. Compounds 7 l, 7m and 7n were found to display the most effective activity against five sensitive strains (0.06–2 μg/mL) and three resistant strains (0.25–4 μg/mL). The kinetic profiles indicated that compound 7l possessed the strongest bactericidal effect on S. aureus ATCC25923, with the MBC value of 16 μg/mL. The cell morphology and the FtsZ polymerization assays indicated that these compounds inhibited the bacterial proliferation by interfering the function of bacterial FtsZ. The SARs showed that all the 4-methyl-substituted 5-methyl-2-phenylphenanthridium subseries could be further investigated as the FtsZ-targeting antibacterial agents.
Suzuki-miyaura cross-coupling reaction catalyzed by 4,4'-tbu2-2,2'- dipyridyl-palladium(II) dichloride complex in aqueous solvent under aerobic condition
Mkhalid,Al-Shaikh
, p. 2077 - 2082 (2014)
4 4'-di-tBu-2 2'-dipyridylpalladium(II) dichloride complex [(tBubpy)PdCl2] showed high efficiency for the Suzuki coupling reaction of aryl iodide and bromide with phenylboronic acid in alcohol solvent under aerobic condition. All reactions gave the isolated coupling products in moderate to excellent yields.
Carbocation-like reactivity patterns in X′-substituted-4-biphenylylnitrenium ions
Ren,McClelland
, p. 78 - 84 (1998)
4-Azido-X′-substituted biphenyls (X′ = 4′-MeO, 4′-Me, 4′-F, 3′-Me, 4′-Cl, H, 3′-MeO, 3′-Cl, 4′-CF3) have been prepared and subjected to 248 nm flash photolysis irradiation in 20:80 acetonitrile:water. Transient X′-substituted 4-biphenylylnitrenium ions 10 (Ar-C6H4-N+H) are observed, with lifetimes ranging from 0.6 ms (4′-MeO) to 26 ns (4′-CF3). These cations are quenched by azide ion, with values of kaz ranging from 6 to 10×109 M-1 s-1, with the majority in the range (9-10)×109. This near constant kaz provides further evidence that arylnitrenium ions are quenched by azide ion at the diffusion limit. The solvent reactivities, plotted in a single-parameter Hammett plot against σ+(X), exhibit a poor correlation, with the points for the para π-electron donors deviating from the correlation line based on the other substituents in the direction of requiring a more negative substituent parameter. The data are more satisfactorily fit to the two-parameter Yukawa-Tsuno equation; the parameter r+ obtained in this fit is 2.8. Thus the resonance interaction of the para π-donor X′-substituents with the positive charge of the cation is underestimated by σ+, a situation that has previously been observed with benzylic-type carbenium ions. The conclusion is made that, in their reaction with water, 4-biphenylylnitrenium ions behave like benzyl cations bearing two additional stabilizing vinyl groups, i.e., as if they had the structure Ar-C+(C-to-C)2 double bond. The inherent reactivity and the pattern of the aryl substituent effects are in fact similar to those in the carbocation series Ar-C+(Ph)2.
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Parish,Whiting
, p. 4713,4716 (1964)
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The Rational Design and Synthesis of Water-Soluble Thiourea Ligands for Recoverable Pd-Catalyzed Aerobic Aqueous Suzuki-Miyaura Reactions at Room Temperature
Chen, Wei,Lu, Xiao-Yan,Xu, Bei-Hua,Yu, Wei-Guo,Zhou, Zi-Niu,Hu, Ying
, p. 1499 - 1510 (2018)
Eight precatalysts containing carboxylic-functionalized thiourea ligands are prepared and their activities and recyclability are evaluated in aerobic aqueous Suzuki-Miyaura reactions. A bulky monothiourea-Pd complex, functionalized with four carboxylic groups, shows the best activity and recyclability in the coupling of aryl bromides with arylboronic acids. The catalyst can be reused at least five times without any significant reduction in its catalytic activity. TEM analysis and the confirmed catalytic activity of the observed black precipitate reveal that Pd nanoparticles are formed during the reactions and are stabilized by the carboxylic-functionalized thiourea ligands.
Selective Carbon-Carbon Bond Amination with Redox-Active Aminating Reagents: A Direct Approach to Anilines?
Qiu, Xu,Wang, Yachong,Su, Lingyu,Jin, Rui,Song, Song,Qin, Qixue,Li, Junhua,Zong, Baoning,Jiao, Ning
supporting information, p. 3011 - 3016 (2021/09/13)
Amines are among the most fundamental motifs in chemical synthesis, and the introduction of amine building blocks via selective C—C bond cleavage allows the construction of nitrogen compounds from simple hydrocarbons through direct skeleton modification. Herein, we report a novel method for the preparation of anilines from alkylarenes via Schmidt-type rearrangement using redox-active amination reagents, which are easily prepared from hydroxylamine. Primary amines and secondary amines were prepared from corresponding alkylarenes or benzyl alcohols under mild conditions. Good compatibility and valuable applications of the transformation were also displayed.
Chemoselective reduction of nitroarenes with hydrazine over a highly active alumina-supported cobalt nanocatalyst
Albadi, Jalal,Samimi, Heshmat Allah,Jalali, Mehdi
, p. 740 - 744 (2019/10/14)
A green and efficient procedure is reported for the chemoselective reduction of nitroarenes catalyzed by a highly active alumina-supported cobalt nanocatalyst in the presence of hydrazine hydrate. The nanocatalyst can be applied under mild reflux conditions for the synthesis of arlyamines in high yields. Moreover, the catalyst can be easily recovered by simple filtration and reused several times without obvious loss in its catalytic activity.
