- A Pd/Cu-Free magnetic cobalt catalyst for C-N cross coupling reactions: synthesis of abemaciclib and fedratinib
-
Herein, the synthesis of a nano-catalytic system comprising magnetic nanoparticles as the core and edible natural ligands bearing functional groups as supports for cobalt species is described. Subsequent to its characterization, the efficiency of the catalyst was investigated for C-N cross-coupling reactions using assorted derivatives of amines and aryl halides. This novel and easily accessible Pd- and Cu-free catalyst exhibited good catalytic activity in these reactions using γ-valerolactone (GVL) at room temperature; good recyclability bodes well for the future application of this strategy. The introduced catalytic system is attractive in view of the excellent efficiency in an array of coupling reactions and its versatility is illustrated in the synthesis of abemaciclib and fedratinib, which are FDA-approved new and significant anti-cancer medicinal compounds that are prepared under green reaction conditions.
- Hajipour, Abdol R.,Khorsandi, Zahra,Sarfjoo, Mohamad Reza,Varma, Rajender S.
-
supporting information
p. 5222 - 5229
(2021/07/29)
-
- Copper nanoparticle anchored biguanidine-modified Zr-UiO-66 MOFs: a competent heterogeneous and reusable nanocatalyst in Buchwald-Hartwig and Ullmann type coupling reactions
-
We have designed a functionalized metal-organic framework (MOF) of UiO topology as a support, with an extremely high surface area, adjustable pore sizes and stable crystalline coordination polymeric structure and implanted copper (Cu) nanoparticles thereon. The core three dimensional Zr-derived MOF (UiO-66-NH2) was modified with a biguanidine moiety following a covalent post-functionalization approach. The morphological and physicochemical features of the material were determined using analytical methods such as FT-IR, SEM, TEM, EDX, atomic mapping, XRD and ICP-OES. The SEM and XRD results justified the unaffected morphology of Zr-MOF after structural modifications. The as-synthesized UiO-66-biguanidine/Cu nanocomposite was catalytically explored in the aryl and heteroaryl Buchwald-Hartwig C-N and Ullmann type C-O cross coupling reactions with excellent yields. A library of biaryl amine and biaryl ethers was synthesized over the catalyst under mild and green conditions. Furthermore, the catalyst was isolated by centrifugation and recycled 11 times with no significant copper leaching or change in its activity.
- Veisi, Hojat,Neyestani, Narges,Pirhayati, Mozhgan,Ahany Kamangar, Sheida,Lotfi, Shahram,Tamoradi, Taiebeh,Karmakar, Bikash
-
p. 22278 - 22286
(2021/07/02)
-
- Integrating CuO?Fe2O3 Nanocomposites and Supramolecular Assemblies of Phenazine for Visible-Light Photoredox Catalysis
-
A photoredox catalytic ensemble consisting of CuO-Fe2O3 nanocomposites and oligomeric derivative of phenazine has been developed. The prepared system acts as an efficient photoredox catalyst for C?N bond formation reaction via SET mechanism under ‘green’ conditions (aerial environment, mixed aqueous media, recyclable), requiring less equivalents of base and amine substrate. The present study demonstrates the significant role of supramolecular assemblies as photooxidants and reductants upon irradiation and their important contribution towards the activation of the metallic centre through energy transfer and electron transfer pathways. The potential of oligomer 4: CuO-Fe2O3 has also been explored for C?C bond formation reactions via the Sonogashira protocol.
- Kaur, Lovjot,Deol, Harnimarta,Kumar, Manoj,Bhalla, Vandana
-
supporting information
p. 892 - 898
(2020/03/04)
-
- Cu(i) based catalysts derived from bidentate ligands and studies on the effect of substituents for: N -arylation of benzimidazoles and indoles
-
A family of Cu(i) complexes [Cu(L1-4)(Cl)(PPh3)] (C1-C4) were synthesized from bidentate ligands L1-L4 (where L1 = (E)-2-(2-benzylidene-1-phenylhydrazinyl)pyridine, L2 = (E)-N,N-dimethyl-4-((2-phenyl-2-(pyridin-2-yl)hydrazono)methyl)aniline, L3 = (E)-2-(2
- Kumari, Sheela,Ratnam, Anand,Mawai, Kiran,Chaudhary, Virendra Kumar,Mohanty, Aurobinda,Ghosh, Kaushik
-
p. 19591 - 19597
(2020/12/05)
-
- Iron oxide encapsulated by copper-Apatite: An efficient magnetic nanocatalyst for: N-Arylation of imidazole with boronic acid
-
N-Arylation of imidazole was carried out with various arylboronic acids on iron oxide encapsulated by copper-Apatite (Fe3O4?Cu-Apatite), producing excellent yields. Firstly, the iron nanoparticles were prepared using a solvothermal m
- Amadine, Othmane,Essamlali, Younes,Amedlous, Abdallah,Zahouily, Mohamed
-
p. 36471 - 36478
(2019/11/20)
-
- Structure Ligation Relationship of Amino Acids for the Amination Cross-Coupling Reactions
-
The structure ligation relationship (SLR) of amino acids (AAs) for the cross-coupling aminations was examined. While AA ligated C-N cross-couplings under Pd and Ni catalysis were minor or ineffective, the AA ligated Cu-catalyzed C-N cross-couplings were promising particularly with the use of l-methionine. The roles of -NH2, -CO2H, and -S- of l-methionine were investigated and found critical for their ligation efficiency. The finding was compatible with aromatic as well as aliphatic amines including tautomerizable N-heteroarenes.
- Vaidya, Gargi Nikhil,Khan, Arif,Verma, Hansa,Kumar, Sanjeev,Kumar, Dinesh
-
p. 3004 - 3010
(2019/03/07)
-
- Ultrafine hybrid Cu2O-Fe2O3 nanoparticles stabilized by hexaphenylbenzene-based supramolecular assemblies: A photocatalytic system for the Ullmann-Goldberg coupling reaction
-
Ultrafine hybrid Cu2O-Fe2O3 NPs have been prepared using the supramolecular assemblies of hexaphenylbenzene (HPB) derivative 3 as nanoreactors and stabilizers. The as-prepared hybrid Cu2O-Fe2O3 NPs serve as an efficient and recyclable photocatalytic system for carrying out C-N coupling between aryl halides and various amines (aliphatic, aromatic and N-heterocyclic) at room temperature in mixed aqueous media under visible light irradiation. Amazingly, Cu2O-Fe2O3 NPs also exhibited high efficiency in the reactions involving the synthesis of biologically important N-substituted carbazole derivatives. The work being presented in this article demonstrates the preparation of a 'dip strip' coated with the as-prepared catalytic system and utilization of this paper strip as a recyclable and portable heterocatalytic system for carrying out the Ullmann-Goldberg coupling.
- Singh, Gurpreet,Kumar, Manoj,Bhalla, Vandana
-
p. 5346 - 5357
(2018/12/05)
-
- A waste-minimized protocol for copper-catalyzed Ullmann-type reaction in a biomass derived furfuryl alcohol/water azeotrope
-
We report the use of biomass-derived furfuryl alcohol as an effective bidentate ligand able to promote the Ullmann-type copper-catalyzed coupling of aryl halides with heteroaromatic or aliphatic amines. Furfuryl alcohol (FA) can be mixed with water to form the corresponding azeotrope (20 wt% of FA) and therefore can be easily recovered and reused. This protocol is efficiently applied to substrates with various electronic nature and affords the expected products (27 examples) in generally good to excellent yields. It has also been demonstrated that the protocol is both chemically and environmentally effective as the azeotropic mixture can be easily and almost quantitatively recovered at the end of the process.
- Ferlin, Francesco,Trombettoni, Valeria,Luciani, Lorenzo,Fusi, Soliver,Piermatti, Oriana,Santoro, Stefano,Vaccaro, Luigi
-
supporting information
p. 1634 - 1639
(2018/04/12)
-
- Base-promoted nucleophilic fluoroarenes substitution of C–F bonds
-
With the use of KOH/DMSO as the superbase medium, the nucleophilic fluoroarene substitution for C–F bonds is presented. The transformation proceeds smoothly with the use of fluoroarenes bearing not only electron-withdrawing group, but also electron-donating group and a variety of nucleophiles such as alcohols, phenols, amines, amides and nitrogen-heterocyclic compounds. The double nucleophilic substitution using ortho-difluoroarenes and nucleophiles bearing ortho-dinucleophilic groups results in the formation of 2,3-dihydro-1,4-benzodioxins, dibenzo[b,e][1,4]dioxins and 10H-phenoxazines in moderate to good yields.
- Su, Ji,Chen, Qian,Lu, Le,Ma, Yuan,Auyoung, George Hong Lok,Hua, Ruimao
-
supporting information
p. 303 - 307
(2017/12/11)
-
- Unique CuI-pyridine based ligands catalytic systems for N-arylation of indoles and other heterocycles
-
Two pyridine-based ligands (N-((pyridin-2-yl) methyl) pyridin-2-amine) L1 and (N-((pyridin-2-yl) methylene) pyridin-2-amine) L2 are explored in present work which are inexpensive, effective and environmentally benign in their properties. These have been utilized for C-N cross coupling reaction resulting in N-arylation. The N-arylation of indole, imidazole and triazole have been successfully carried out with different aryl and heteroaryl halides using these ligands.
- Taywade, Amol,Chavan, Snehal,Ulhe, Avinash,Berad, Baliram
-
supporting information
p. 1443 - 1453
(2018/06/01)
-
- Copper nanoparticles incorporated on a mesoporous carbon nitride, an excellent catalyst in the Huisgen 1,3-dipolar cycloaddition and N-arylation of N-heterocycles
-
Cu nanoparticles with average particles size around 10?nm were incorporated on the surface of a mesoporous carbon nitride support. The XRD and N2 adsorption isotherms show that it maintains a hexagonal mesoporous structure with a high surface a
- Kazemi Movahed, Siyavash,Salari, Parinaz,Kasmaei, Melika,Armaghan, Mahsa,Dabiri, Minoo,Amini, Mostafa M.
-
-
- CopperII phthalocyanine as an efficient and reusable catalyst for the N-arylation of nitrogen containing heterocycles
-
Copper phthalocyanine (CuIIPc) was found to be an efficient catalyst for the catalyzed N-arylation of N–H heterocycles with aryl iodides and bromides under mild reaction conditions. A variety of hindered and functionalized N–H heterocycles and aryl halides were successfully used as the substrates for the given catalytic reaction and were transformed in good to excellent yields.
- Yadav, Kumar Karitkey,Narang, Uma,Bhattacharya, Soumee,Chauhan, Shive M.S.
-
supporting information
p. 3044 - 3048
(2017/07/17)
-
- Copper(I) Oxide/N,N′-Bis[(2-furyl)methyl]oxalamide-Catalyzed Coupling of (Hetero)aryl Halides and Nitrogen Heterocycles at Low Catalytic Loading
-
An easily prepared oxalic diamide is a powerful ligand for the copper-catalyzed coupling of aryl halides with nitrogen heterocycles. Only 1–2 mol% each of copper(I) oxide and N,N′-bis[(2-furyl)methyl]oxalamide (BFMO) are needed to form N-arylation products under mild conditions. More than 10 different types of nitrogen heterocycles are compatible with these conditions, thereby giving the corresponding N-arylation products. (Figure presented.).
- Pawar, Govind Goroba,Wu, Haibo,De, Subhadip,Ma, Dawei
-
supporting information
p. 1631 - 1636
(2017/05/22)
-
- INDOLE AND INDAZOLE CYANOCINNAMATE COMPOUNDS AND THERAPEUTIC USES THEREOF
-
Disclosed are Indole and Indazole cyanocinnamate compounds, method for preparing these compounds, and methods for treating cancer.
- -
-
Paragraph 0126-0127; 0128-0129
(2017/12/01)
-
- A carbon nitride supported copper nanoparticle composite: a heterogeneous catalyst for the N-arylation of hetero-aromatic compounds
-
A graphitic carbon nitride supported copper nanoparticle composite (Cu-gCN) has been found to be an active catalyst for the N-arylation of hetero-aromatic systems (pyrrole, pyrazole, and substituted indole) and benzamide molecules, with high product selectivity and good to excellent yields, using substituted aryl bromide as a coupling partner. The intercalated structure and the amine functional group of the carbon nitride prevent the aggregation of the catalytically active copper species during the reaction, and the recyclability study shows the stable performance of the catalyst without a significant loss of catalytic activity.
- Nandi, Debkumar,Siwal, Samarjeet,Mallick, Kaushik
-
supporting information
p. 3082 - 3088
(2017/04/14)
-
- N-Picolinamides as ligands for Ullmann-type C-N coupling reactions
-
The use of N-phenyl-2-pyridincarboxamide-1-oxide as a ligand with Cu2O in Ullmann type C-N bond formations between aryl halides and N-heteroaryls in common solvents, such as MeCN, DMF, and DMSO at 82-120 °C has been successfully demonstrated. The ligand is effective when only 4% equiv is used relative to the substrate. The reaction provided the corresponding products in coupling of electron-rich, electron poor, and ortho-substituted aryl halides, including ortho aryl-chlorides, in good to very good yields. N-arylation is selectively preferred at the benzyl position when ortho-halide benzyl bromide is reacted with one equivalent of pyrazole. However, di-N-arylation is achieved in very high yields when 2.5 equiv of pyrazole is used, providing a stoichiometric control over the coupling reaction.
- Damkaci, Fehmi,Alawaed, Abdulkhaliq,Vik, Erik
-
supporting information
p. 2197 - 2200
(2016/05/02)
-
- A 1,10-phenanthrene rowling-N-Monoxide derivatives ligand and its application
-
The invention relates to a 1,10-Phenanthroline monohydrate-dual N-monoxide derivative ligand. The derivative ligand has a structural formula as follows: FORMULA, wherein R1 and R8 are selected from hydrogen, halogen, hydroxyl, C1-C7 alkoxyl, straight-chain saturated or unsaturated C1-C6 alkyl, or branched-chain saturated or unsaturated C1-C6 alkyl; R2 to R7 are selected from hydrogen, halogen, hydroxyl, C1-C8 alkoxyl, straight-chain saturated or unsaturated C1-C6 alkyl, or branched-chain saturated or unsaturated C1-C6 alkyl, C3-C7 ring hydroxyl, benzyl, aryl or 5-7 membered heterocyclic ring. Hetero atoms (such as O or N) are contained in the ligand disclosed by the invention, and a transitional six-membered ring is formed through coordination with copper ions, so that aryl iodide, aryl bromide or aryl chloride is promoted to carry out a C-N coupling reaction with aliphatic amine or secondary aliphatic cyclammonium or aliphatic acid or nitrogen-containing heterocyclic compounds at room temperature.
- -
-
Paragraph 0342-0353
(2016/11/21)
-
- Pd immobilized on modified magnetic Fe3O4 nanoparticles: Magnetically recoverable and reusable Pd nanocatalyst for Suzuki-Miyaura coupling reactions and Ullmann-type N-arylation of indoles
-
The Pd supported on amidoxime (AO)-functionalized Fe3O4 (Fe3O4/AO/Pd) hybrid material was used as an effective and recyclable nanocatalyst in Suzuki-Miyaura coupling reactions. The catalyst was very effective for the Suzuki-Miyaura reaction of aryl halides (Ar–I, Ar–Br, Ar–Cl) with phenylboronic acid and conversion was excellent in most cases. The yields of the products were in the range from 7–98%. The catalyst showed good stability and could be recovered and reused for six reaction cycles without a significant loss in its catalytic activity. Also, a wide range of N-arylated indoles are selectively synthesized through intermolecular C(aryl)–N bond formation from the corresponding aryl iodides and indoles through Ullmann-type coupling reactions in the presence of the prepared catalyst. [Figure not available: see fulltext.]
- Ghorbani-Vaghei, Ramin,Hemmati, Saba,Hekmati, Malak
-
p. 1157 - 1162
(2016/07/15)
-
- Efficient and recyclable copper-based MOF-catalyzed N-arylation of N-containing heterocycles with aryliodides
-
Copper-based MOF-199 was used as an efficient heterogeneous catalyst to catalyze cross-coupling reactions between N-containing heterocycles and aryliodides with high yields. The catalyst can be easily separated from the reaction mixture, and can be reused at least 5 times without significantly decreasing the activity. The XRD results showed that the crystallinity and structure of MOF-199 can be maintained well during the coupling reaction.
- Li, Zihao,Meng, Fei,Zhang, Jie,Xie, Jianwei,Dai, Bin
-
supporting information
p. 10861 - 10865
(2016/12/06)
-
- Carbon nitride supported palladium nanoparticles: An active system for the reduction of aromatic nitro-compounds
-
Synthesis of carbon nitride supported highly dispersed ultrafine palladium nanoparticles has been reported for the reduction of aromatic nitro-compounds using hydrazine hydrate as a reducing agent. As a demonstration, the as-synthesized carbon nitride-palladium composite was shown to be a highly active and chemo-selective for the title reaction. Utilizing the optimized reaction conditions a set of aromatic nitro compounds have been converted to their corresponding amine derivatives with good to excellent yield ranging from 80% to 99%. The catalyst can be used for multiple times without affecting the catalytic performance and can also be stored for a long time at ambient condition maintaining the high catalytic efficiency.
- Nandi, Debkumar,Siwal, Samarjeet,Choudhary, Meenakshi,Mallick, Kaushik
-
-
- Copper(I) 3-methylsalicylate mediates the Chan-Lam N-arylation of heterocycles
-
Copper(I) 3-methylsalicylate (CuMeSal) mediates N-arylation reactions between aryl boronic acids and aromatic heterocycles (Chan-Lam coupling) under moderate reaction conditions (K2CO3, methanol, 65 °C, in air, 3-5 h). Both electron-rich and electron-deficient aryl boronic acids and a diverse set of N-heterocycles were allowed to react and gave N-arylation products in reasonable yields, which demonstrate the utility of this catalyst.
- Farahat, Abdelbasset A.,Boykin, David W.
-
supporting information
p. 245 - 252
(2015/10/29)
-
- Tamarix gallica leaf extract mediated novel route for green synthesis of CuO nanoparticles and their application for N-arylation of nitrogen-containing heterocycles under ligand-free conditions
-
We report the green synthesis of CuO nanoparticles (CuO NPs) using Tamarix gallica leaf extract and their catalytic activity for N-arylation of nitrogen-containing heterocycles with aryl halides under ligand-free conditions. Tamarix gallica leaves are used as a bio-material for the first time as reducing agent. The green synthesized CuO NPs was characterized using the powder XRD, TEM, UV-vis and FT-IR. This method offers several advantages, viz. high yields, simple methodology, recyclability of the catalyst and a simple workup procedure.
- Nasrollahzadeh, Mahmoud,Sajadi, S. Mohammad,Maham, Mehdi
-
p. 40628 - 40635
(2015/05/20)
-
- A green, homogeneous and reusable surfactant/copper based ionic liquid for the N-arylation of indoles, pyrazoles and imidazoles
-
An efficient surfactant/copper based ionic liquid promoter was examined as a reusable system for the N-arylation of indole, pyrazole and imidazole by a variety of aryl halides. The products were obtained in good to excellent yields by a convenient one-pot procedure. The reaction could be carried out in water under air and did not require the use of arylboronic acids as the active aryl source, palladium as the catalyst or a strong base.
- Heidarizadeh, Fariba,Majdi-Nasab, Afrooz
-
p. 6360 - 6363
(2015/11/16)
-
- SBA-15-functionalized melamine-pyridine group-supported palladium(0) as an efficient heterogeneous and recyclable nanocatalyst for N-arylation of indoles through Ullmann-type coupling reactions
-
SBA-15-functionalized melamine-pyridine group-supported palladium(0) was found to serve as a heterogeneous and recyclable nanocatalyst for N-arylation of indoles with aryl iodides under a low catalyst loading (0.3mol% of Pd) through Ullmann-type C£N coupling reactions. A variety of aryl iodides could be aminated to provide the N-arylated products in good to excellent yields without the need of an inert atmosphere. Also, this catalyst was found to be an efficient system for the N-arylation of other nitrogen-containing heterocycles with aryl iodides. The heterogeneous palladium catalyst could be recovered by simple filtration of the reaction solution and reused for six cycles without significant loss in its activity.
- Veisi, Hojat,Poor Heravi, Mohammad Reza,Hamelian, Mona
-
p. 334 - 337
(2015/04/27)
-
- Palladium nanoparticles supported on modified single-walled carbon nanotubes: A heterogeneous and reusable catalyst in the Ullmann-type N-arylation of imidazoles and indoles
-
Air- and moisture-stable and recyclable palladium nanoparticles supported on modified single-walled carbon nanotubes (SWCNT-Met/Pd) behave as very efficient heterogeneous catalysts in the Ullmann coupling of imidazoles and indoles with aryl iodides to afford the corresponding C-N coupling reactions under aerobic conditions. These cross coupled products were produced in excellent yields at low palladium loading (~0.2 mol%) and the heterogeneous catalyst can be readily recovered by simple filtration and reused five times without a noticeable loss in its catalytic activity.
- Veisi, Hojat,Morakabati, Nekoo
-
p. 2901 - 2907
(2015/04/14)
-
- Metal-free regioselective C-3 acetoxylation of N-substituted indoles: Crucial impact of nitrogen-substituent
-
A metal-free method for the regioselective C-3 acetoxylation of the N-substituted indoles with PhI(OAc)2 is described under mild reaction conditions. This method tolerates a broad range of functional groups with moderate to good yields. The π-e
- Soni, Vineeta,Patel, Ulhas N.,Punji, Benudhar
-
p. 57472 - 57481
(2015/07/20)
-
- Maghemite-Copper Nanocomposites: Applications for Ligand-Free Cross-Coupling (C-O, C-S, and C-N) Reactions
-
A magnetically retrievable, efficient, and benign maghemite-Cu nanocatalyst was synthesized from inexpensive precursors and applied for C-O, C-N, and C-S bond-formation reactions. The obtained maghemite-Cu nanocatalyst was characterized by various techniques such as XRD, X-ray photoelectron spectroscopy, field-emission gun SEM with energy-dispersive spectroscopy, atomic absorption spectroscopy, TEM, high-angle annular dark-field scanning transmission electron microscopy, FTIR spectroscopy, and M?ssbauer spectroscopy. Excellent catalytic activity, ease of recovery, and reusability without a significant loss of yield make the present protocol highly sustainable to deal with industrial and environmental concerns. Magnetic attraction: A magnetically retrievable, efficient, and benign maghemite-Cu nanocatalyst is synthesized from inexpensive precursors and applied for C-O, C-N, and C-S bond-formation reactions. Excellent catalytic activity, ease of recovery, and reusability without significant loss of yield make the present protocol highly sustainable to deal with industrial and environmental concerns.
- Sharma, Rakesh K.,Gaur, Rashmi,Yadav, Manavi,Rathi, Anuj K.,Pechousek, Jiri,Petr, Martin,Zboril, Radek,Gawande, Manoj B.
-
p. 3495 - 3502
(2015/11/10)
-
- Design, synthesis and structure - activity relationship of oxazolidinone derivatives containing novel S4 ligand as FXa inhibitors
-
Abstract A novel series of potent and efficacious factor Xa inhibitors which possesses pyrrole/indole/thiazole moieties as S4 binding element was identified. Compound 7b showed strong human factor Xa inhibitory activity (IC50 = 2.01 nM) and ant
- Zhao, Yanfang,Jiang, Mingyan,Zhou, Shunguang,Wu, Shasha,Zhang, Xiaolong,Ma, Longsheng,Zhang, Kai,Gong, Ping
-
p. 369 - 380
(2015/05/05)
-
- Copper nanoparticle decorated organically modified montmorillonite (OMMT): An efficient catalyst for the N-arylation of indoles and similar heterocycles
-
A highly active ligand-free and efficient copper nanoparticle decorated OMMT catalyzed N-arylation of NH-heterocycles, i.e. indole, imidazole, benzimidazole, pyrrole, carbazole has been demonstrated.
- Talukdar, Dhrubajyoti,Das, Gautam,Thakur, Suman,Karak, Niranjan,Thakur, Ashim J.
-
p. 238 - 243
(2015/02/19)
-
- Base-mediated N- And O-arylations of NH-containing heterocycles, heterocyclic amines and phenols
-
Nucleophilic substitution reactions of N-heterocycles such as imidazole, benzimidazole, indole and pyrazole as well as NH2 or OH containing heterocycles, with electron-deficient aryl halides in the presence of t-BuOK or K2CO3as base and DMSO as solvent are reported. A series of N-aryl azoles, unsymmetric diaryl ethers and diaryl amines were obtained in good yields.
- Ghasemi, Zarrin,Shahrak, Nasim Shahi,Roomi, Behzad Jalali,Zakeri, Ziba
-
-
- KOtBu-mediated aerobic transition-metal-free regioselective β-arylation of indoles: Synthesis of β-(2-/4-Nitroaryl)-indoles
-
A KOtBu-mediated intermolecular oxidative C-C coupling of nitroarenes with indoles is presented in DMSO at room temperature in an open flask. By using this mild and economical methodology, syntheses of β-(2/4-nitroaryl)-indoles with sensitive f
- Kumar, Shailesh,Rathore, Vandana,Verma, Ajay,Prasad, Ch. Durga,Kumar, Amit,Yadav, Abhimanyu,Jana, Sadhan,Sattar, Moh.,Meenakshi,Kumar, Sangit
-
supporting information
p. 82 - 85
(2017/01/17)
-
- KOtBu-Mediated Aerobic Transition-Metal-Free Regioselective β-Arylation of Indoles: Synthesis of β-(2-/4-Nitroaryl)-indoles
-
A KOtBu-mediated intermolecular oxidative C-C coupling of nitroarenes with indoles is presented in DMSO at room temperature in an open flask. By using this mild and economical methodology, syntheses of β-(2/4-nitroaryl)-indoles with sensitive f
- Kumar, Shailesh,Rathore, Vandana,Verma, Ajay,Prasad, Ch. Durga,Kumar, Amit,Yadav, Abhimanyu,Jana, Sadhan,Sattar, Moh,Meenakshi,Kumar, Sangit
-
supporting information
p. 82 - 85
(2015/07/28)
-
- Palladium on carbon-catalyzed one-pot N-arylindole synthesis: Intramolecular aromatic amination, aromatization, and intermolecular aromatic amination
-
Indole and indoline derivatives were selectively and temperature dependently synthesized via the intramolecular cross-coupling reaction between the amino and aromatic bromine functionalities of 2-bromophenethylamine derivatives in the presence of 10% palladium on carbon (Pd/C), 1,1-bis(diphenylphosphino)ferrocene (DPPF), and sodium tert-butoxide (NaO-t-Bu) in mesitylene at 140 and 200°C, respectively. The neutralization using acetic acid after formation of the indoline derivatives effectively promoted their aromatization, and the corresponding indole derivatives were obtained at 140°C. Furthermore, various aryl groups were also introduced to the N-1 position of the indole, pyrrole, and carbazole rings by their direct intramolecular arylation with aryl halides and a one-pot protocol for N-arylindole synthesis from 2-bromophenethylamine was developed.
- Monguchi, Yasunari,Marumoto, Takahisa,Takamatsu, Haruki,Sawama, Yoshinari,Sajiki, Hironao
-
p. 1866 - 1872
(2014/06/09)
-
- Highly active recyclable heterogeneous Pd/ZnO nanoparticle catalyst: Sustainable developments for the C-O and C-N bond cross-coupling reactions of aryl halides under ligand-free conditions
-
Efficient Pd supported on ZnO nanoparticles for the ligand-free O-arylation and N-arylation of phenols and various N-H heterocycles with aryl chlorides, bromides, and iodides were readily synthesized and characterized. The amount of palladium on ZnO is 9.84 wt% (0.005 g of the catalyst contains 462 × 10-8 mol% of Pd) which was determined by ICP analysis. This nano sized Pd/ZnO with an average particle size of 20-25 nm and specific surface area 40.61 m2 g-1 was used as a new reusable heterogeneous catalyst for the formation of C-O and C-N bonds in organic synthesis. This protocol gives the arylated product in satisfactory yields without any N2 or Ar flow. The catalyst can be recovered and recycled several times without marked loss of activity.
- Hosseini-Sarvari, Mona,Razmi, Zahra
-
p. 44105 - 44116
(2014/12/10)
-
- New ligands for copper-catalyzed C-N coupling reactions at gentle temperature
-
Pyridin-2-ol-N-oxide was designed as an efficient ligand for the coupling reaction of aryl iodides, aryl bromides and aryl chlorides, respectively, with primary amines, cyclic secondary amines or N-containing heterocycles at room or moderate temperature. The catalytic system showed great functional groups tolerance and excellent selective reactivity.
- Su, Jinyue,Qiu, Yatao,Jiang, Sheng,Zhang, Dayong
-
supporting information
p. 685 - 688
(2014/10/15)
-
- Synthesis of 1-aryl indoles via coupling reaction of indoles and aryl halides catalyzed by CuI/metformin
-
Ullmann-type C-N coupling reaction has been developed for the synthesis of 1-aryl indole derivatives by indoles and aryl halides in the presence of CuI/metformin (CuI/Met) in DMF. This method is very easy, rapid, and high yielding reaction for the synthesis of 1-aryl indoles. In particular, the metformin, which is used as ligand, is inexpensive and nontoxic that is considered to be relatively environmentally benign.
- Chen, Hu,Lei, Min,Hu, Lihong
-
p. 5626 - 5631
(2015/03/30)
-
- A reusable polystyrene-supported copper(II) catalytic system for N-arylation of indoles and Sonogashira coupling reactions in water
-
A polymer-anchored Cu(II) N,N-dimethylethylenediamine complex was prepared and characterized by various techniques, including Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), atomic absorption spectroscopy (AAS), and thermogravimetric analysis (TGA). This heterogeneous Cu(II) catalyst, efficiently works for the N-arylation of indoles and Sonogashira coupling of terminal alkynes with aryl halides in aqueous medium. The effect of solvent, and base for the C-N, and C-C coupling reactions were reported. Further, the catalyst can be easily recovered quantitatively by simple filtration and reused up to four times without significant loss of its catalytic activity.
- Kodicherla, Balaswamy,Perumgani C., Pullaiah,Mandapati, Mohan Rao
-
p. 110 - 115
(2014/08/18)
-
- An efficient, mild and selective Ullmann-type N-arylation of indoles catalysed by Pd immobilized on amidoxime-functionalized mesoporous SBA-15 as heterogeneous and recyclable nanocatalyst
-
A wide range of N-arylated indoles were selectively synthesized through intermolecular C(aryl)-N bond formation from the corresponding aryl iodides and indoles through Ullmann-type coupling reactions in the presence of a catalytic amount of Pd immobilized on amidoxime-functionalized mesoporous SBA-15 (SBA-15/AO/Pd(0)) under mild reaction conditions. These cross-coupled products were obtained in excellent yields under mild conditions at extremely low palladium loading (ca 0.3 mol%), and the heterogeneous catalyst can be readily recovered by simple filtration and reused seven times with loss in its activity.
- Ghorbani-Vaghei, Ramin,Hemmati, Saba,Hamelian, Mona,Veisi, Hojat
-
p. 195 - 199
(2015/03/30)
-
- Copper(I) 3-methylsalicylate, an efficient catalyst for N-arylation of heterocycles under moderate reaction conditions
-
Copper(I) 3-methylsalicylate mediates N-arylation reactions of both aliphatic and aromatic heterocycles under moderate reaction conditions. Both electron rich and electron poor aryl bromides and a diverse set of N-heterocycles were allowed to react and gave N-arylation products in high yields which demonstrated the efficiency and utility of this catalyst.
- Farahat, Abdelbasset A.,Boykin, David W.
-
supporting information
p. 3049 - 3051
(2014/05/20)
-
- A one-step method for preparation of Cu@Cu2O nanoparticles on reduced graphene oxide and their catalytic activities in N-arylation of N-heterocycles
-
Core-shell Cu@Cu2O nanoparticles on reduced graphene oxide (Cu@Cu2O NPs-RGO) nanocomposite were prepared at room temperature by in situ reduction of graphene oxide (GO) and copper sulfate using l-ascorbic acid as reducing agent and t
- Movahed, Siyavash Kazemi,Dabiri, Minoo,Bazgir, Ayoob
-
-
- MCM-41-immobilized bidentate nitrogen copper(I) complex: A highly efficient and recyclable catalyst for Buchwald N-arylation of indoles
-
The heterogeneous N-arylation reaction of indoles with aryl halides was achieved in toluene at 110 C by using 4 mol % MCM-41-immobilized bidentate nitrogen copper(I) complex [MCM-41-2N-CuI] as catalyst and K3PO 4 as base, yielding a variety of N-arylindoles in good to excellent yields. The heterogeneous copper catalyst exhibited as high activity as homogeneous CuI/diamine catalytic system and can be easily prepared by a simple two-step procedure from commercially available and cheap reagents and recovered by a simple filtration of the reaction solution and reused for 10 cycles with almost consistent activity.
- Xiao, Ruian,Zhao, Hong,Cai, Mingzhong
-
p. 5444 - 5450
(2013/06/27)
-
- Aqueous copper-catalyzed N-arylation of indoles: The surfactant strategy
-
Surfactants have long been underestimated in synthetic organic chemistry despite their great potential in promoting solubility, reactivity and selectivity in metal-mediated cross-couplings. In this study the strategy of surfactant promotion was exemplified in copper-catalyzed N-arylation of indoles in water. The different effects of surfactants during the coupling reaction were first explored. The superior promoting effect of the natural zwitterionic surfactant, betaine, was found and attributed to the capability of the formed complex to stabilize the copper intermediate in the catalytic transformation and facilitate transportation of the reactants. The concept of surfactant promotion through complexation is valuable in metal-mediated cross-couplings. This method also exhibited good recycling ability. This study will greatly facilitate exploration of surfactant promotion in metal-mediated cross-couplings.
- Liu, Songbai,Zhou, Jiahui
-
supporting information
p. 2537 - 2540
(2013/09/24)
-
- Solvent- and ligand-free palladium-catalyzed amination of aryl halides
-
An environmentally friendly and economically favorable approach to the formation of C-N bonds is presented. The methodology is particularly interesting in that the reaction is realized under both solvent- and ligand-free conditions and involves the use of
- Basolo, Luca,Bernasconi, Alice,Broggini, Gianluigi,Gazzola, Silvia,Beccalli, Egle M.
-
p. 3151 - 3156
(2013/12/04)
-
- New ligands for copper-catalyzed C-N coupling reactions with aryl halides
-
2-Carbomethoxy-3-hydroxyquinoxaline-di-N-oxide was identified as an efficient novel ligand for the copper-catalyzed coupling reactions of aryl iodides, bromides, and chlorides with aliphatic amines and N-containing heterocycles under mild conditions. The catalytic system showed great functional-group tolerance and excellent chemoselectivity. 7copy; 2012 Elsevier Ltd. All rights reserved.
- Chen, Dong,Yang, Kai,Xiang, Hua,Jiang, Sheng
-
supporting information
p. 7121 - 7124
(2013/01/15)
-
- Green synthesis of predominant (1 1 1) facet CuO nanoparticles: Heterogeneous and recyclable catalyst for N-arylation of indoles
-
Well faceted CuO nanoparticles were synthesized by thermal-assisted green strategy at reflux temperature in a short period of time. A possible growth mechanism of such highly faceted nanostructures based on typical biomolecule-crystal interactions in aque
- Suramwar, Nikhil V.,Thakare, Sanjay R.,Karade, Nandkishor N.,Khaty, Niren T.
-
experimental part
p. 28 - 34
(2012/07/14)
-
- Nano ceria catalyzed Ullmann type coupling reactions
-
Ullmann type intermolecular coupling of aryl halide with hetero-aromatic compounds, such as phenols, amines, and thiophenols are key reactions for the formation of carbon-heteroatom bond in organic synthesis. We report a robust and novel method that provides an efficient and economic route for the synthesis of O, N, and S-arylation via Ullman coupling by using nano cerium oxide (ceria, CeO2). CeO2 is a cheaper catalyst compared to related copper based catalysts. This method provides a wide range of substrate applicability in the case of phenols and amines. Less reactive chlorobenzene substituted with strong electron withdrawing groups such as 4-nitrochlorobenzene and 4-cyanochlorobenzene favor the reaction. This protocol avoids the use of ligand and gives arylated product in satisfactory yields.
- Agawane, Sandeep M.,Nagarkar, Jayashree M.
-
experimental part
p. 5220 - 5223
(2011/10/12)
-
- Ligands for copper-catalyzed C-N bond forming reactions with 1 Mol% CuBr as catalyst
-
Several new ligands were designed to promote copper-catalyzed Ullman C-N coupling reactions. In this group, 8-hydroxyquinolin-N-oxide was found to serve as a superior ligand for CuBr-catalyzed coupling reactions of aryl iodides, bromides, and chlorides with aliphatic amines and N-heterocycles under a low catalyst loading (1% [Cu] mol). Reactions with the inexpensive catalytic system display a high functional group tolerance as well as excellent chemoselectivity.
- Yang, Kai,Qiu, Yatao,Li, Zheng,Wang, Zhaoyang,Jiang, Sheng
-
experimental part
p. 3151 - 3159
(2011/06/23)
-
- Efficacy of C-N coupling reactions with a new multinuclear copper complex catalyst and its dissociation into mononuclear species
-
A new tetranuclear copper(I)-pyridazine (pda)/rhenate hybrid has been synthesized under hydrothermal conditions and structurally characterized by X-ray crystallography. The activity of this catalyst, as well as its dissociation into mononuclear species, was investigated in homogeneous C-N arylation reactions. A variety of N-arylamides and-azoles were synthesized in good to excellent yields, revealing the effect of polynuclear versus mononuclear Cu complexation in this type of coupling reaction.
- Zou, Yan,Lin, Haisheng,Maggard, Paul A.,Deiters, Alexander
-
experimental part
p. 4154 - 4159
(2011/10/04)
-
- Directed synthesis and immunoactive properties of (2-hydroxyethyl)ammonium salts of 1-R-indol-3-ylsulfanyl(sulfonyl)alkanecarboxylic acids
-
A general method for the synthesis of 1-alkyl(allyl)(benzyl)-substituted (indol-3-yl)-sulfanylalkanecarboxylic acids and hexane-1,6-diyl(1,4- phenylenemethylene)bisindol-3-ylsulfanylalkanecarboxylic acids from the corresponding N-substituted indoles and bisindoles, thiourea, iodine, and halogencarboxylic acids was developed. The oxidation of substituted (indol-3-yl)sulfanylalkanecarboxylic acids for the first time afforded their analogs containing the sulfonyl group. New (2-hydroxyethyl)ammonium salts of 1-R-indol-3-ylsulfanyl(sulfonyl)-alkanecarboxylic acids, which are structural analogs of highly active immunomodulators of indacetamin and VILIM, were synthesized. Among the studied (2-hydroxyethyl)ammonium salts of 1-R-indol-3-ylsulfanylacetic and -sulfonylalkanecarboxylic acids, the compounds exhibiting high dose-dependent antiproliferative activity by the ability to affect the spontaneous and mitogen-stimulated splenocyte proliferation of mice in vitro were found.
- Mirskova,Levkovskaya,Kolesnikova,Perminova,Rudyakova,Adamovich
-
experimental part
p. 2236 - 2246
(2011/08/05)
-
- Copper iodide as a recyclable catalyst for Buchwald N-arylation
-
An experimentally simple, efficient, and inexpensive catalyst system was developed for the N-arylation of indole, substituted indoles, pyrazole, imidazole, benzamide, morpholine, benzimidazole, thiobenzamide, aniline, benzylaniline, octylaniline, heptylaniline, and cyclohexylaniline with aryl iodides and bromides by using CuI as catalyst, trans-1,2-diaminocyclohexane (L1) as ligand, K2CO3 as base, and water as solvent at 80 °C. The yields were excellent, and the catalytic system was recyclable up to four times without loss of catalytic activity. Arylated amines are green protocol that avoids hazardous and moisture-sensitive catalysts. The catalytic system can be recycled up to four times without loss of catalytic activity. Copyright
- Swapna, Kokkirala,Murthy, Sabbavarapu Narayana,Nageswar, Yadavalli Venkata Durga
-
experimental part
p. 6678 - 6684
(2011/02/25)
-