- Selectivities in Reactions of Organolithium Reagents with Aryl Bromides Which Bear Proton-Donating Groups
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Studies of substrates which offer an acidic hydrogen and an aryl bromide for reaction with an organolithium reagent have been carried out with a series of benzene bromo amides and bromo anilides as well as selected benzene bromo carboxylic acids, bromoanilines, and bromobenzylamines.A representative example is the reaction of N-ethyl-N-deutero-o-bromobenzamide (6-d) with 1-lithio-3-phenylpropane to give N-ethyl-o-deuterobenzamide (46percent, 94percent-d) (7-d), N-ethyl-o-bromobenzamide (6) (49percent), 3-deutero-1-phenylpropane (51percent, 92percent-d), and 1-bromo-3-phenylpropane (48percent).Product formation in this and related cases is explained by the operation of a two step sequence in which an initial deprotonation is followed by a bromine-lithium exchange which is accelerated with respect to mixing.Such a sequence is consistent with the results of deuterium labeling and with changes in product ratios on different mixing and with differently aggregated organolithium reagents.Support is provided for the operation of two pathways for the expedited bromine-lithium exchange reactions.In one pathway a high local concentration of the organolithium reagent promotes rapid reaction and in the second the exchange reaction occurs within an initially formed complex.The selectivity for removal of a bromine ortho to a lithiated carboxamide is found to be 5-8 with n-butyllithium, and satisfactory synthetic ortho selectivity is obtained for N-ethyl-2,5-dibromobenzamide with phenyllithium.
- Beak, Peter,Musick, Timothy J.,Liu, Chao,Cooper, Thomas,Gallagher, Donald J.
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- Synthesis of N -Aryl Amides by Ligand-Free Copper-Catalyzed ipso -Amidation of Arylboronic Acids with Nitriles
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A facile copper-catalyzed ipso-amidation of arylboronic acids with nitriles has been developed. The method provides a highly efficient and economical synthesis of N-aryl amides with a broad substrate scope.
- Qiao, Yan,Li, Gaoqiang,Liu, Sha,Yangkai, Yujie,Tu, Jingxuan,Xu, Feng
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- Synthesis of pyrimido[2,1-a]isoindolone and isoindolo[2,1-a]quinazolinoneviaintramolecular aza-Prins type reaction
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A novel aza-Prins type cyclization reaction involvingN-acyliminium ions and amides is reported for the synthesis of tetrahydropyrimido[2,1-a]isoindole-2,6-dione and 6,6a-dihydroisoindolo[2,1-a]quinazoline-5,11-dione derivatives in excellent yields. The strategy features inexpensive reagents, mild reaction conditions, and metal-free synthesis of N-heterocyclic frameworks. Further, post-synthetic modification results in the unprecedented formation of its triazole, tetracyclic diazacyclopenta[def]phenanthrene-1,4(9a1H)-dione and carbonyl derivatives.
- Biswas, Subhamoy,Porashar, Bikoshita,Arandhara, Pallav Jyoti,Saikia, Anil K.
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supporting information
p. 11701 - 11704
(2021/11/12)
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- Iron-catalyzed oxidative amidation of acylhydrazines with amines
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A new approach for amide bond formation via a mild and efficient Iron-catalyzed cross-coupling reaction of acylhydrazines and amines using TBHP as oxidant is described. This protocol is compatible with a wide range of amines and acylhydrazines. In addition, the synthetic application of the reaction is presented.
- Wang, Yi-Jie,Zhang, Guo-Yu,Shoberu, Adedamola,Zou, Jian-Ping
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- Organocatalyst in Direct C(sp2)-H Arylation of Unactivated Arenes: [1-(2-Hydroxyethyl)-piperazine]-Catalyzed Inter-/Intra-molecular C-H Bond Activation
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This article describes the identification of 1-(2-hydroxyethyl)-piperazine as a new, cost-effective, highly efficient organocatalyst, which promotes both inter- A nd intra-molecular direct C(sp2)-H arylations of unactivated arenes in the presence of potassium tert-butoxide. While the inter-molecular C-H arylation of unactivated benzenes with aryl halides (Ar-X; X = I, Br, Cl) toward biaryl syntheses underwent smoothly in the presence of only 10 mol percent organocatalyst, the intra-molecular C-H arylation catalytic system composed of 40 mol percent each of the catalyst and the additive (4-dimethylaminopyridine (DMAP)). The novel catalyst was also able to perform both inter- A nd intra-molecular direct arylations simultaneously in a single pot. The mechanistic studies confirmed the involvement of aryl radical anions and proceeded via a single-electron-transfer (SET) mechanism. The large substrate scope, high functional group tolerance, competition experiments, gram-scale synthesis, and kinetic studies further highlight the importance and versatile nature of the methodology as well as the compatibility of the new catalyst. To the best of our knowledge, this is the first report on any organocatalyst that reported detailed investigations of both inter- A nd intra-molecular direct C(sp2)-H arylations of unactivated arenes in a single representation.
- Yadav, Lalit,Tiwari, Mohit K.,Shyamlal, Bharti Rajesh Kumar,Chaudhary, Sandeep
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p. 8121 - 8141
(2020/07/16)
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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 0018-0028
(2019/10/01)
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- Palladium-catalyzed intramolecular C-H arylation of 2-halo-: N -Boc- N -arylbenzamides for the synthesis of N-H phenanthridinones
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A palladium catalyzed synthesis of N-H phenanthridinones was developed via C-H arylation. The protocol gives phenanthridinones regioselectively by one-pot reaction without deprotection. It exhibits broad substrate scope and affords targets in up to 95% yields. Importantly, it could be applied for the less reactive o-chlorobenzamides.
- Hu, Quan-Fang,Gao, Tian-Tao,Shi, Yao-Jie,Lei, Qian,Yu, Luo-Ting
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p. 13879 - 13890
(2018/04/25)
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- Transfer Hydro-dehalogenation of Organic Halides Catalyzed by Ruthenium(II) Complex
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A simple and efficient Ru(II)-catalyzed transfer hydro-dehalogenation of organic halides using 2-propanol solvent as the hydride source was reported. This methodology is applicable for hydro-dehalogenation of a variety of aromatic halides and α-haloesters and amides without additional ligand, and quantitative yields were achieved in many cases. The potential synthetic application of this method was demonstrated by efficient gram-scale transformation with catalyst loading as low as 0.5 mol %.
- You, Tingjie,Wang, Zhenrong,Chen, Jiajia,Xia, Yuanzhi
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p. 1340 - 1346
(2017/02/10)
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- Synthesis and antibacterial activity of 5-methylphenanthridium derivatives as FtsZ inhibitors
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5-Methylphenanthridium derivatives were designed, synthesized and evaluated for their in vitro antibacterial activity and cell division inhibitory activity against various Gram-positive and -negative bacteria. Among them, compounds 5A2, 5B1, 5B2, 5B3, 5C1 and 5C2 displayed the best on-target antibacterial activity with an MIC value of 4?μg/mL against B. subtilis ATCC9372 and S. pyogenes PS, showing over 2-fold better activity than sanguinarine. The SARs showed that the 5-methylphenanthridium derivatives with the alkyl side chains at the 2-postion, especially the straight alkyl side chains exerted better on-target antibacterial activity.
- Liu, Fang,Venter, Henrietta,Bi, Fangchao,Semple, Susan J.,Liu, Jingru,Jin, Chaobin,Ma, Shutao
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supporting information
p. 3399 - 3402
(2017/07/07)
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- Acidylation method of amine
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The invention discloses an acidylation method of amine.The method includes the following steps that amine derivatives, hydrazide derivatives, organic peroxide and a catalyst are dissolved in a solvent and react at the temperature of 40-80 DEG C, and amide derivatives are obtained.The amide derivatives and hydrazide derivatives serve as initiators, the raw materials are easy to obtain and the number of varieties is large.Products obtained through the method are diverse in type, can be directly used and can also be used for other further reactions.The method is mild in reaction condition, simple in reaction operation and post-processing process, high in product yield and suitable for scale production.
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Paragraph 0047
(2016/10/10)
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- Practical Synthesis of Phenanthridinones by Palladium-Catalyzed One-Pot C-C and C-N Coupling Reaction: Extending the Substrate Scope to o-Chlorobenzamides
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A highly efficient construction of phenanthridinone derivatives from o-halobenzamides was developed by using a phosphine-free palladium catalyst in N,N-dimethylacetamide. The domino reaction proceeds through a sequential C-C and C-N bond-formation process in one pot. This protocol exhibits broad substrate scope and affords a series of phenanthridinones in up to 93 % yield. Importantly, the protocol could also be applied for the less reactive o-chlorobenzamides. The approach constitutes the first example of the synthesis of phenanthridinones from this kind of substrate. Moreover, the success of a gram-scale reaction demonstrated that this operationally simple process is scalable.
- Liu, Hailong,Han, Weibiao,Li, Chun,Ma, Zhiyong,Li, Ruixiang,Zheng, Xueli,Fu, Haiyan,Chen, Hua
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supporting information
p. 389 - 393
(2016/02/18)
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- Synthesis of 1-aminoisoquinolines by gold(III)-mediated domino reactions from 2-alkynylbenzamides and ammonium acetate
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A facile synthetic route toward pharmaceutically interesting 1-aminoisoquinoline derivatives by gold(III)-mediated domino reactions is described. This synthetic protocol starts from readily available 2-alkynylbenzamides and ammonium acetate and takes plac
- Long, Yuhua,She, Zhigang,Liu, Xiaochen,Chen, Yu
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p. 2579 - 2588
(2013/04/24)
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- Palladium-catalyzed C-C coupling of aryl halides with isocyanides: An alternative method for the stereoselective synthesis of (3E)-(Imino)isoindolin- 1-ones and (3E)-(imino)thiaisoindoline 1,1-dioxides
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A palladium-catalyzed, one-pot cyclization reaction to construct (3E)-(imino)isoindolin-1-ones and (3E)-(imino)thiaisoindoline 1,1-dioxides by introducing ortho-reactive functional groups on aryl halides is reported. Under optimal conditions, the cyclization reaction afforded the corresponding products in good to excellent yields (up to 93%) with high stereoselectivity. Notably, this transformation successfully extends its application for the synthesis of phenanthridines and dibenzooxazepines. This new synthetic protocol not only extends the application platform for palladium-catalyzed C-C coupling of aryl halides with isocyanides, but also opens atom-economic and step-economic synthetic routes for nitrogen-containing heterocyclic compounds with wide functional group compatibility. Copyright
- Liu, Bifu,Li, Yibiao,Jiang, Huanfeng,Yin, Meizhou,Huang, Huawen
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p. 2288 - 2300
(2012/11/07)
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- Microwave assisted copper-free Sonogashira coupling/5-exo-dig cycloisomerization domino reaction: Access to 3-(phenylmethylene)isoindolin-1- ones and related heterocycles
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An efficient microwave assisted one-pot synthesis of substituted 3-(phenylmethylene)isoindolin-1-ones is reported via a copper-free Sonogashira coupling and a regioselective 5-exo-dig cycloisomerization. This domino reaction was also extended to other related heterocycles.
- Hellal, Malik,Cuny, Gregory D.
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supporting information; experimental part
p. 5508 - 5511
(2011/10/31)
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- Highly efficient amide synthesis from alcohols and amines by virtue of a water-soluble gold/DNA catalyst
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Gold takes to water: The synthesis of amides directly from alcohols and amines was realized by using a water-soluble Au/DNA nanohybrid as the catalyst. The interactions between the gold nanoparticles, DNA, and water lead to high catalytic efficiency under mild reaction conditions. The wide substrate scope includes less-basic aromatic amines, and this catalyst is recyclable.
- Wang, Ye,Zhu, Dapeng,Tang, Lin,Wang, Sujing,Wang, Zhiyong
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supporting information; experimental part
p. 8917 - 8921
(2011/10/31)
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- ANTIOXIDANTS AND METHODS OF THEIR USE
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The invention relates to compounds and compositions to treat some neurodegenerative diseases. In some embodiments, the invention relates to an antioxidant comprising a selenium atom and nitroxide group. In further embodiments, the antioxidant comprises peroxidase and superoxide dismutase activity. In some embodiments, the antioxidants are effective in treating neurodegenerative diseases including, but not limited to, Alzheimer's disease, Parkinson's disease, or multiple sclerosis. In additional embodiments, the invention relates to using compounds disclosed herein as free radical electromagnetic imaging agents.
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Page/Page column 71-72
(2010/11/28)
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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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- Diazotisation Rearrangement of Tosylhydrazones of ortho- and meta-Substituted-benzophenones and α-Substituted-acetophenones (Synthesis of Anilides)
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Ortho and meta-substituted-benzophenones (1a-g) and substituted-acetophenones (1h-i) were converted into tosylhydrazones (2a-i) by reacting with p-toluenesulphonyl-hydrazide.Conversion of 2a-i to the anilides (3a-i) was effected with the reagents H2SO4 and NaNO2, and was found to be as facile as in case of the para-substituted-benzophenone hydrozones.
- Joshi, Vidya,Sharma, R. K.
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p. 564 - 566
(2007/10/02)
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