- Copper-catalyzed Goldberg-type C-N coupling in deep eutectic solvents (DESs) and water under aerobic conditions
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An efficient and selectiveN-functionalization of amides is first reportedviaa CuI-catalyzed Goldberg-type C-N coupling reaction between aryl iodides and primary/secondary amides run either in Deep Eutectic Solvents (DESs) or water as sustainable reaction media, under mild and bench-type reaction conditions (absence of protecting atmosphere). Higher activities were observed in an aqueous medium, though the employment of DESs expanded and improved the scope of the reaction to include also aliphatic amides. Additional valuable features of the reported protocol include: (i) the possibility to scale up the reaction without any erosion of the yield/reaction time; (ii) the recyclability of both the catalyst and the eutectic solvent up to 4 consecutive runs; and (iii) the feasibility of the proposed catalytic system for the synthesis of biologically active molecules.
- Cicco, Luciana,Hernández-Fernández, Jose A.,Salomone, Antonio,Vitale, Paola,Ramos-Martín, Marina,González-Sabín, Javier,Presa Soto, Alejandro,Perna, Filippo M.,Capriati, Vito,García-álvarez, Joaquín
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- Visible-Light-Promoted Iron-Catalyzed N-Arylation of Dioxazolones with Arylboronic Acids
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A visible-light-promoted and simple iron salt-catalyzed N-arylation was achieved efficiently under external photosensitizer-free conditions. Arylboronic acids and bench-stable dioxazolones were used for this cross-coupling reaction. This reaction features high reactivity, wide substrate scope, good functional group tolerance, simple operation procedure, and mild reaction conditions. Preliminary mechanistic investigations were conducted to support a radical pathway. This method may contribute to shift the paradigm of iron-catalyzed C-N bond construction and nitrene transfer chemistry.
- Tang, Jing-Jing,Yu, Xiaoqiang,Yamamoto, Yoshinori,Bao, Ming
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p. 13955 - 13961
(2021/11/20)
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- Metal-free transamidation of benzoylpyrrolidin-2-one and amines under aqueous conditions
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N-Acyl lactam amides, such as benzoylpyrrolidin-2-one, benzoylpiperidin-2-one, and benzoylazepan-2-one reacted with amines in the presence of DTBP and TBAI to afford the transamidated products in good yields. The reactions were conducted under aqueous conditions and good functional group tolerance was achieved. Both aliphatic and aromatic primary amines displayed good activity under metal-free conditions. A radical reaction pathway is proposed.
- Joseph, Devaneyan,Lee, Sunwoo,Park, Myeong Seong
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supporting information
p. 6227 - 6232
(2021/07/28)
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- Exploration of Cu-catalyzed regioselective hydrodehalogenation of o-haloanilides using EtOH as hydrogen source
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In present work, we have explored a Cu(acac)2/vasicine-catalyzed regioselective hydrodehalogenation methodology of o-haloanilides using EtOH as hydrogen source and solvent. The catalytic system could selectively dehalogenate 2-Br and 2-I, and features regioselective, efficient and functional group tolerance.
- Li, Min-Xin,Li, Mei-Ling,Tang, Yan-Ling,Sun, Yun,Qu, Lu,Huang, Feng,Mao, Ze-Wei
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supporting information
(2021/05/03)
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- Visible-Light Carbon Nitride-Catalyzed Aerobic Cyclization of Thiobenzanilides under Ambient Air Conditions
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A metal-free heterogeneous photocatalysis has been developed for the synthesis of benzothiazoles via intramolecular C-H functionalization/C-S bond formation of thiobenzanilides by inexpensive graphitic carbon nitride (g-C3N4) under visible-light irradiation. This reaction provides access to a broad range of 2-substituted benzothiazoles in high yields under an air atmosphere at room temperature without addition of a strong base or organic oxidizing reagents. In addition, the catalyst was found to be stable and reusable after five reaction cycles.
- Bai, Jin,Yan, Sijia,Zhang, Zhuxia,Guo, Zhen,Zhou, Cong-Ying
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supporting information
p. 4843 - 4848
(2021/06/28)
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- Efficient Pd-Catalyzed Hydrodehalogenation of o -Haloanilides in Water
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In the present work, we have developed a practical methodology for the hydrodehalogenation of o -haloanilides using PdCl 2at 100 °C under mild conditions in water. The catalytic system could selectively dehalogenate both aryl chloride and aryl bromide and exhibit a broad functional group tolerance.
- Gao, Hui,Li, Minxin,Mao, Zewei,Rao, Gaoxiong,Tang, Yanling
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supporting information
p. 1121 - 1125
(2020/07/03)
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- Nickel-Catalyzed C-F/N-H Annulation of Aromatic Amides with Alkynes: Activation of C-F Bonds under Mild Reaction Conditions
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The Ni-catalyzed reaction of ortho-fluoro-substituted aromatic amides with alkynes results in C-F/N-H annulation to give 1(2H)-isoquinolinones. A key to the success of the reaction is the use of KOtBu or even weak base, such as Cs2CO3. The reaction proceeds in the absence of a ligand and under mild reaction conditions (40-60 °C). DFT calculations suggest that the pathway for this Ni-catalyzed C-F/N-H annulation involves N-H deprotonation, oxidative addition of a C-F bond, migratory insertion of an alkyne, and reductive elimination to form 1(2H)-isoquinolinone derivatives.
- Bai, Ruopeng,Chatani, Naoto,Lan, Yu,Liu, Song,Nohira, Itsuki
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supporting information
p. 17306 - 17311
(2020/11/13)
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- Methyl Esters as Cross-Coupling Electrophiles: Direct Synthesis of Amide Bonds
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Amide bond formation and transition metal-catalyzed cross-coupling are two of the most frequently used chemical reactions in organic synthesis. Recently, an overlap between these two reaction families was identified when Pd and Ni catalysts were demonstrated to cleave the strong C-O bond present in esters via oxidative addition. When simple methyl and ethyl esters are used, this transformation provides a powerful alternative to classical amide bond formations, which commonly feature stoichiometric activating agents. Thus far, few redox-active catalysts have been demonstrated to activate the C(acyl)-O bond of alkyl esters, which makes it difficult to perform informed screening when a challenging reaction needs optimization. We demonstrate that Ni catalysts bearing diverse NHC, phosphine, and nitrogen-containing ligands can all be used to activate methyl esters and enable their use in direct amide bond formation.
- Zheng, Yan-Long,Newman, Stephen G.
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p. 4426 - 4433
(2019/05/08)
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- Chromium-Catalyzed Activation of Acyl C-O Bonds with Magnesium for Amidation of Esters with Nitroarenes
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Here, we report a chromium-catalyzed activation of acyl C-O bonds with magnesium for amidation of esters with nitroarenes. Low-cost chromium(III) chloride shows high reactivity in promoting amidation by using magnesium as reductant and chlorotrimethylsilane as additive. It provides a step-economic strategy to the synthesis of centrally important amide motifs using inexpensive and air-stable nitroarenes as amino sources.
- Ling, Liang,Chen, Changpeng,Luo, Meiming,Zeng, Xiaoming
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supporting information
(2019/03/19)
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- Synthesis of amides from acid chlorides and amines in the bio-based solvent Cyrene
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Cyrene as a bio-alternative dipolar aprotic solvent: a waste minimizing and molar efficient protocol for the synthesis of amides from acid chlorides and primary amines in the bio-available solvent Cyrene is disclosed. This protocol removed the use of toxic solvents, such as dimethylformamide and dichloromethane. A simple aqueous work-up procedure for the removal of the high boiling solvent Cyrene resulted in up to a 55-fold increase in molar efficiency (Mol E.%) versus standard operating procedures. In order to rapidly compare the molar efficiency of this process against other methodologies an Excel based Mol. E% calculator was developed that automates many of the calculations. An investigation into the hydration of Cyrene found that it readily hydrates to form a geminal diol in the presence of water and that this process is exothermic.
- Bousfield, Thomas W.,Pearce, Katharine P. R.,Nyamini, Simbarashe B.,Angelis-Dimakis, Athanasios,Camp, Jason E.
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supporting information
p. 3675 - 3681
(2019/07/09)
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- Exogenous Photosensitizer-, Metal-, and Base-Free Visible-Light-Promoted C-H Thiolation via Reverse Hydrogen Atom Transfer
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Visible-light-driven, intramolecular C(sp2)-H thiolation has been achieved without addition of a photosensitizer, metal catalyst, or base. This reaction induces the cyclization of thiobenzanilides to benzothiazoles. The substrate absorbs visible light, and its excited state undergoes a reverse hydrogen-atom transfer (RHAT) with 2,2,6,6-tetramethylpiperidine N-oxyl to form a sulfur radical. The addition of the sulfur radical to the benzene ring gives an aryl radical, which then rearomatizes to benzothiazole via RHAT.
- Xu, Ze-Ming,Li, Hong-Xi,Young, David James,Zhu, Da-Liang,Li, Hai-Yan,Lang, Jian-Ping
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supporting information
p. 237 - 241
(2019/01/10)
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- Method for synthesizing amide compound through photocatalysis in water phase
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The invention discloses a method for synthesizing an amide compound through photocatalysis in a water phase. The method comprises the following steps: putting catalysis amounts of a free radical initiator, an amine derivative, a carboxylic acid derivative, a phase transfer catalyst, an inorganic base and water into a reaction container, carrying out a reaction in a photocatalysis reaction instrument at certain power under a room temperature condition, after a certain time, carrying out extraction by using a small amount of ethyl acetate, and carrying out recrystallization, so as to obtain theamide compound, wherein the free radical initiator is eosin, methyl orange, sodium persulfate, ammonium persulfate or potassium peroxodisulfate, the phase transfer catalyst is tetrabutylammonium bromide, and the power of the photocatalytic reaction instrument is 5W. By adopting the method disclosed by the invention, toxic thionyl chloride or phosphorus oxychloride is not needed for a chlorinationreaction, water is adopted as a solvent, a novel photocatalysis method is used, and the amide compound with a high yield can be prepared through a room-temperature reaction for 2-5 hours with an incandescent light bulb of 5W, and in addition, the method is simple in aftertreatment, and low in cost and is an ideal green synthesis method of amide compounds.
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Paragraph 0018-0026
(2019/10/01)
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- Detection of weak hydrogen bonding to fluoro and nitro groups in solution using H/D exchange
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Hydrogen/deuterium (H/D) exchange can be a sensitive technique for measuring the strength of hydrogen bonding to neutral organic nitro and fluoro groups. The slower rates of reaction in comparison to suitable controls suggest that hydrogen bonding is present, albeit rather weak.
- Shugrue,Defrancisco,Metrano,Brink,Nomoto,Linton
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supporting information
p. 2223 - 2227
(2016/03/01)
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- An efficient magnetic copper ferrite nanoparticle catalysed ligand and solvent free synthesis of N-aryl amide from aldoximes and iodobenzene
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A simple, efficient, and environmentally benign method has been reported for the synthesis of N-aryl amides using aldoximes and iodobenzene under ligand free and solvent free conditions and using magnetically separable copper ferrite nanoparticles as catalyst. The catalyst was characterised using XRD, FEG-SEM, EDAX, ICP-AES and TEM and tested for recyclability for up to five cycles.
- Sarode, Sachin A.,Bhojane, Jeevan M.,Nagarkar, Jayashree M.
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p. 105353 - 105358
(2015/12/30)
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- Efficient cobalt-catalyzed C-N cross-coupling reaction between benzamide and aryl iodide in water
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A practical and efficient strategy for the N-arylation of benzamide catalysed by a Co(C2O4)·2H2O/dmeda system in water is reported. Under the optimized conditions, a wide variety of N-arylated products were obtained in good yields (up to 92%) using substituted aryl iodides.
- Tan, Bryan Yong-Hao,Teo, Yong-Chua
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supporting information
p. 7478 - 7481
(2014/12/11)
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- Copper-catalyzed direct oxidation and N-arylation of benzylamines with diaryliodonium salts
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An efficient approach for the synthesis of N-arylated amides was developed via copper(II) triflate-catalyzed direct oxidation of (aryl)methylamines to primary arylamides by air and subsequent N-arylation by diaryliodonium salts. Various substituted benzylamines could be applied in the reaction, providing a series of N-arylated amides in moderate to good yields. This method showed convenient, practical, and environment friendly advantages.
- Liu, Xin,Mao, Dan,Wu, Shengying,Yu, Jianjun,Hong, Gang,Zhao, Qiao,Wang, Limin
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p. 1132 - 1136
(2014/08/18)
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- The synthesis of N-arylated amides via copper(II) triflate-catalyzed direct oxygenation and N-arylation of benzylamines with aryl iodides
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An efficient approach for the synthesis of N-arylated amides by copper(II) triflate-catalyzed direct oxygenation and N-arylation reaction of benzylamines with aryl iodides is reported. Various benzylamines and aryl iodides can participate in the reaction, providing a series of N-arylated amides in moderate to good yields.
- Xu, Mei,Zhang, Xiao-Hong,Shao, Yin-Lin,Han, Jiang-Sheng,Zhong, Ping
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supporting information
p. 2665 - 2670,6
(2012/12/12)
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- The synthesis of N-arylated amides via copper(II) triflate-catalyzed direct oxygenation and N-arylation of benzylamines with aryl iodides
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An efficient approach for the synthesis of N-arylated amides by copper(II) triflate-catalyzed direct oxygenation and N-arylation reaction of benzylamines with aryl iodides is reported. Various benzylamines and aryl iodides can participate in the reaction, providing a series of N-arylated amides in moderate to good yields.
- Xu, Mei,Zhang, Xiao-Hong,Shao, Yin-Lin,Han, Jiang-Sheng,Zhong, Ping
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supporting information
p. 2665 - 2670
(2013/01/15)
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- A simple copper-catalyzed synthesis of tertiary acyclic amides
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The N-arylation of aromatic and aliphatic secondary acyclic amides, known to be poor nucleophiles, has been accomplished using a simple and cheap copper catalytic system. The corresponding tertiary acyclic amides, which can be found in numerous biologically active compounds, have been obtained in good to excellent yields.
- Racine, Emilie,Monnier, Florian,Vors, Jean-Pierre,Taillefer, Marc
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supporting information; experimental part
p. 2818 - 2821
(2011/07/09)
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- Conjugate addition - SNAr domino reaction for the synthesis of benzo- or pyridyl-fused lactams and sultams
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A versatile domino reaction that can be used for the synthesis of bicyclic benzo- or pyridyl-fused lactam and sultam derivatives is presented, enabling rapid synthesis of a variety of complex structures
- Norager, Niels Gron,Juhl, Karsten
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experimental part
p. 4273 - 4281
(2011/02/22)
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- An efficient route to 3-aminoindazoles and 3-amino-7-azaindazoles
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A non-acidic procedure for the preparation of 3-aminoindazoles and 3-amino-7-azaindazoles from 2-fluoroaryl carboxylic acids is reported. The synthesis starts from readily available starting materials and uses mild and practical reaction conditions in a three-step overall procedure. Products were isolated for a number of examples, but yields varied significantly depending on electronic nature of the substituents.
- Burke, Michael J.,Trantow, Brian M.
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p. 4579 - 4581
(2008/09/21)
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- A series of new zirconium complexes bearing bis(phenoxyketimine) ligands: Synthesis, characterization and ethylene polymerization
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A series of new zirconium complexes bearing bis(phenoxyketimine) ligands, bis((3,5-di-tert-butyl-C6H2-2-O)R1CN (2-R 2-C6H4))ZrCl2 {R1 = Me, R2 = H (2a); R1 = Et, R2 = H (2b); R 1 = Ph, R2 = H (2c); R1 = 2-Me-Ph, R 2 = H (2d); R1 = 2-F-Ph, R2 = H (2e); R 1 = 2-Cl-Ph, R2 = H (2f); R1 = 2-Br-Ph, R 2 = H (2g); R1 = Ph, R2 = Me (2h); R 1 = Ph, R2 = F (2i)}, have been prepared, characterized and tested as catalyst precursors for ethylene polymerization. Crystal structure analysis reveals that complex 2c has a six coordinate center in a distorted octahedral geometry with trans-O, cis-N, cis-Cl arrangement which possesses approximate C2 symmetry. When activated with methylaluminoxane (MAO), complexes 2a-2i exhibited high ethylene polymerization activities of 10 6-108 g PE (mol M h)-1. Compared with the bis(phenoxyimine) zirconium analogues bis((3,5-di-tert-butyl-C6H 2-2-O)CHNC6H5)ZrCl2 (3), the introduction of substituent on the carbon atom of the imine double bond enhanced the catalytic activity and molecular weight of prepared polyethylene. Especially, when the H atom at the carbon atom of the imine double bond was replaced by 2-fluoro-phenyl with strong electronic-withdrawing property, complex 2e displayed the highest catalytic activity, and the polyethylene obtained possessed the highest molecular weight and melt point.
- Chen, Shangtao,Zhang, Xiaofan,Ma, Hongwei,Lu, Yingying,Zhang, Zhicheng,Li, Huayi,Lu, Zhanxia,Cui, Nannan,Hu, Youliang
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p. 4184 - 4191
(2007/10/03)
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- Control of the fading properties of photochromic 3,3-diaryl-3H-naphtho[2,1-b]pyrans
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The synthesis and spectroscopic properties of some novel photochromic 3H-naphtho[2,1-b]pyrans are reported. Varying the size of an ortho-substituent on one of the geminal aryl rings allows the rate of fade of the photogenerated color to be controlled.
- Gabbutt, Christopher D.,Heron, B. Mark,Instone, Alicia C.
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p. 843 - 855
(2007/10/03)
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